KR20170082461A - Photosensitive compositions - Google Patents

Abstract

The present invention relates to a photosensitive composition comprising a polyester amide acid having a polymerizable double bond, a compound having a polymerizable double bond other than the polyester amide acid, a photopolymerization initiator, an epoxy compound, and an additive. The polyester amide acid having a polymerizable double bond is obtained by reacting a tetracarboxylic acid dianhydride, a diamine and a polyhydric hydroxy compound as essential raw material components. By using the photosensitive composition of the present invention, a cured film excellent in heat resistance, chemical resistance, adhesion to substrate, transparency, flatness, resolution and residual film ratio can be obtained.

Description

[0001] PHOTOSENSITIVE COMPOSITIONS [0002]

The present invention relates to a photosensitive composition used in various devices, a cured film formed of the photosensitive composition, and a color filter, an insulating film, or a protective film using the cured film.

In a device such as a display element, a chemical treatment or a high-temperature heat treatment is usually performed on the surface of the device during the manufacturing process. Therefore, a protective film is formed to prevent the surface of the device from deterioration, damage, and deterioration. The protective film requires heat resistance, chemical resistance, adhesion to substrates, transparency and flatness, and satisfactory resolution and retention rate.

The protective film is formed by a thermosetting composition and a photosensitive composition, when largely divided. In the case of the thermosetting composition, the volatile matter generated during film formation is suppressed to a small extent and the heat resistance is excellent. However, it is difficult to form a scribe line in the thermosetting composition, and it is necessary to carry out a step of cleaning a residue which occurs at the time of panel division.

On the other hand, in the case of the photosensitive composition, the scribe line is easily formed and the moldability is excellent. For this reason, there is an increasing demand as a protective film for a photosensitive composition capable of fine molding (fine patterning).

In order to form an excellent fine pattern shape, it is necessary to maintain appropriate solubility in the photosensitive composition so as to provide an appropriate balance between the resolution and the residual film ratio. If the solubility of the unexposed portion is increased to improve the resolution, the solubility of the exposed portion is also increased and the residual film ratio is lowered. On the other hand, if the solubility of the exposed portion is lowered to increase the residual film ratio, the solubility of the unexposed portion is also lowered and the resolution is lowered. That is, the photosensitive composition needs to select an appropriate composition ratio so as to increase the solubility of the exposed portion and lower the solubility of the unexposed portion. Therefore, it is difficult to appropriately maintain the relationship between the resolution and the residual film ratio while keeping the composition ratio and composition of the polyester amide acid and the like optimally.

For example, as shown in Patent Documents 1 and 2, a polyimide precursor as a raw material of the photosensitive composition and soluble polyimide require an organic solvent having high polarity in order to increase the solubility. However, when applied to a color filter, Is dissolved in an organic solvent having a high polarity.

Thus, as shown in Patent Document 3, the present inventors have found that when the ratio of polyester amide acid to acid anhydride, diamine and polyhydric hydroxy compound is within a predetermined range, and the total amount of the compound having double bonds, epoxy compound, And is set to a predetermined range. Thus, it has been proposed that the photosensitive composition does not require an organic solvent having a high polarity, and improves the coatability and flatness of the substrate and forms an excellent fine pattern shape.

The inventors of the present invention studied an appropriate relationship between resolution and retention rate by adding a polymerizable double bond as an essential component to the polyester amide acid (A) in order to further improve the moldability of the fine pattern shape.

Japanese Patent Application Laid-Open No. 59-68332 Japanese Patent Application Laid-Open No. 2002-3516 Japanese Patent Application Laid-Open No. 2016-103010

Accordingly, an object of the present invention is to provide a cured film having excellent heat resistance, transparency and flatness, and excellent resolution and residual film ratio, and a photosensitive composition for forming the cured film. Further, a color filter or a protective film using this composition is applied to various uses.

As a result of intensive studies to solve the above problems, the present inventors have found that a photosensitive composition according to the present invention comprises a polyesteramide acid (A) having a polymerizable double bond, a polymerizable double bond other than the polyesteramide acid (B), a photopolymerization initiator (C), an epoxy compound (D) and an additive (E). The polyester amide acid (A) is obtained by reacting a tetracarboxylic acid dianhydride, a diamine and a polyhydric hydroxy compound as essential raw material components.

According to one embodiment of the present invention, the photosensitive composition comprises a polyester amide acid (A) having a polymerizable double bond, a compound (B) having a polymerizable double bond other than the polyester amide acid (A) An initiator (C), an epoxy compound (D), and an additive (E). The polyester amide acid (A) has a ratio of X mole of tetracarboxylic acid dianhydride, Y mole of diamine, and Z mole of polyhydroxy compound satisfying the relationship of the following formulas (1) and (2) ≪ / RTI >

0.2? Z / Y? ... ... (One)

0.2? (Y + Z) /X? 5.0? (2)

The compound (B) contains at least two polymerizable double bonds per molecule, and the epoxy compound (D) contains 2 to 10 epoxy groups per molecule and has a weight average molecular weight of less than 3,000. The total amount of the compound (B) is 20 to 300 parts by weight, and the total amount of the epoxy compound (D) is 20 to 200 parts by weight based on 100 parts by weight of the polyester amide acid (A).

The polyester amide acid (A) has a structural unit represented by the following formula (3) and a structural unit represented by the following formula (4).

In the formulas (3) and (4), R ¹ is a residue obtained by removing two -CO-O-CO- from a tetracarboxylic acid dianhydride, R ² is a residue obtained by removing two -NH ₂ from a diamine, R ³ is a residue obtained by removing two -OH from a polyhydric hydroxy compound. R ¹ , R ² and R ³ in the formula may be independently a single structure or may contain two or more structures, and at least one of R ¹ , R ² and R ³ has a polymerizable double bond.

Embodiments that have In at least one is the polymerizable double bond of R ³ include the aspects that have at least one is the polymerizable double bond, but R ¹ of the formula in the polyester amide acid (A), and R ² May have a polymerizable double bond. At least one of each of two arbitrary residues selected from R ¹ , R ² and R ³ may have a polymerizable double bond, and it may be preferred that all three residues of R ¹ , R ² and R ³ At least one of them may have a polymerizable double bond.

According to another embodiment of the present invention, the polyester amide acid (A) is obtained by reacting X mol of tetracarboxylic acid dianhydride, Y mol of diamine, Z mol of polyhydric hydroxy compound and a monohydroxy compound (1) and (2). ≪ EMI ID = 2.0 >

0.2? Z / Y? ... ... (One)

0.2? (Y + Z) /X? 5.0? (2)

The polyester amide acid (A) has a structural unit represented by the following formula (3), a structural unit represented by the formula (4) and a structural unit represented by the formula (5).

In the formulas (3), (4) and (5), R ¹ is a residue obtained by removing two -CO-O-CO- from a tetracarboxylic acid dianhydride and R ² is a residue obtained by removing two -NH ₂ R ³ is a residue obtained by removing two -OH from a polyhydric hydroxy compound, and R ⁴ is a residue obtained by removing one -OH from a monohydroxy compound. At least one of the expression of the R ^1, R ^2, R ^3, and R ⁴ are independently even a single structure, and may contain two or more structures, R ^1, R ^2, R ^3, and R ⁴ is And has a polymerizable double bond.

In the polyester amide acid (A) described in the paragraph, at least one of R ^{3 in} the formula has a polymerizable double bond, at least one of R ^{4 in} the formula has a polymerizable double bond, At least one of R < ³ > and at least one of R < ⁴ > have a polymerizable double bond. However, it is also possible that at least one of R ¹ has a polymerizable double bond, and that at least one of R ² has a polymerizable double bond. ^{Further, R 1, R 2, R} 3, and being with at least one each of any two residues of selected from R ⁴ even though you have taken suggested embodiment which has a polymerizable double ^{bond, R 1, R 2, R} 3, and R and with at least one respective arbitrary three moieties selected from ⁴ even though you have taken suggested embodiment which has a polymerizable double bond, and, R ^1, R ^2, R ^3, and each of at least 1 for all four residues of R ⁴ May have a polymerizable double bond.

The polyhydric hydroxy compound may be at least one compound selected from the group consisting of ethylene glycol, propylene glycol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, 1,7-heptanediol, Bis (4-hydroxycyclohexyl) propane, 4,4'-dihydroxydicyclohexyl, isocyanuric acid tris (2-hydroxyethyl), 2-hydroxybenzyl alcohol, 4-hydroxybenzyl alcohol, 2 - (4-hydroxyphenyl) ethanol, and a compound having a polymerizable double bond.

The polyhydric hydroxy compound having a polymerizable double bond has a vinyl group, an allyl group, or a (meth) acryloxy group.

The polyhydric hydroxy compound having a polymerizable double bond may be at least one selected from the group consisting of glycerin mono (meth) acrylate, trimethylolpropane mono (meth) acrylate, pentaerythritol mono (meth) acrylate, pentaerythritol di (meth) Acrylate, dipentaerythritol tri (meth) acrylate, dipentaerythritol tetra (meth) acrylate, sorbitol mono (meth) acrylate, dipentaerythritol tri (Meth) acrylic acid modified product of propylene glycol diglycidyl ether, sorbitol di (meth) acrylate, sorbitol tri (meth) acrylate, sorbitol tetra (meth) acrylate, ethylene glycol diglycidyl ether (Meth) acrylic acid modified product, a (meth) acrylic acid modified product of tripropylene glycol diglycidyl ether, a (meth) acrylic acid modified product of glycerin diglycidyl ether (Meth) acrylic acid modified product of bisphenol A diglycidyl ether, a (meth) acrylic acid modified product of propylene oxide-modified bisphenol A diglycidyl ether, and a compound containing two or more epoxy groups per molecule (Meth) acrylic acid modified product.

Wherein the monohydroxy compound is at least one selected from the group consisting of isopropyl alcohol, benzyl alcohol, propylene glycol monoethyl ether, 3-ethyl-3-hydroxymethyloxetane, and a monohydroxy compound having a polymerizable double bond Lt; / RTI >

The monohydroxy compound having a polymerizable double bond has a vinyl group, an allyl group, or a (meth) acryloxy group.

The monohydroxy compound having a polymerizable double bond may be at least one selected from the group consisting of furfuryl alcohol, allyl alcohol, hydroxyethyl (meth) acrylate, hydroxypropyl (meth) acrylate, hydroxybutyl (meth) (Meth) acrylate, 1,4-cyclohexanedimethanol mono (meth) acrylate, 4-hydroxypropyl (meth) acrylate, 4-hydroxyphenyl (Meth) acrylate, pentaerythritol tri (meth) acrylate, dipentaerythritol penta (meth) acrylate, pentaerythritol tri (meth) acrylate, And (meth) acrylic acid modified product of a compound containing one epoxy group per molecule.

The weight average molecular weight of the polyester amide acid (A) is 1,000 to 200,000.

The tetracarboxylic acid dianhydride may be selected from the group consisting of 3,3 ', 4,4'-diphenylsulfone tetracarboxylic acid dianhydride, 3,3', 4,4'-diphenylether tetracarboxylic dianhydride, 2,2- [ Bis (3,4-dicarboxyphenyl)] hexafluoropropane dianhydride, 1,2,3,4-butanetetracarboxylic acid dianhydride, and ethylene glycol bis (anhydrotrimellitate) At least one compound.

The diamine is at least one of 3,3'-diaminodiphenylsulfone and bis [4- (3-aminophenoxy) phenyl] sulfone.

The compound (B) may be at least one compound selected from the group consisting of dipentaerythritol pentaacrylate, dipentaerythritol hexaacrylate, pentaerythritol tetraacrylate, pentaerythritol triacrylate, isocyanuric acid ethylene oxide modified triacrylate, and polybasic acid- ) Acrylic oligomer in an amount of at least 50% by weight based on the total weight of the composition.

The epoxy compound is preferably selected from the group consisting of 3 ', 4'-epoxycyclohexylmethyl-3,4-epoxycyclohexanecarboxylate, 1-methyl-4- (2-methyloxiranyl) -7-oxabicyclo [4.1.0] Phenyl] ethyl] phenyl] propane and a mixture of 2- [4- [1,1-bis [4- (2,3-epoxypropoxy) 1- [4- [1- [4- (2,3-epoxypropoxy) phenyl] -1- [4- [ Phenyl] -2- [4- [1, 1 -bis [4- (2-methoxyphenyl) Phenylpropane, 1,1,1-tris (4-hydroxyphenyl) ethane triglycidyl ether, 1,3-bis (oxiranylmethyl) -5- 2-propenyl) -1,3,5-triazine-2,4,6 (1H, 3H, 5H) -triene, 2,2-bis (hydroxymethyl) Epoxy-4- (2-oxiranyl) cyclohexane adduct.

The photopolymerization initiator (C) is at least one selected from the group consisting of an? -Aminoalkylphenone-based, acylphosphine oxide-based, oxime ester-based photopolymerization initiator.

The additive (E) includes at least one of a coupling agent and a surfactant.

The tetracarboxylic acid dianhydride is at least one of 3,3 ', 4,4'-diphenyl ether tetracarboxylic dianhydride and 1,2,3,4-butanetetracarboxylic dianhydride, and the diamine is 3 , 3'-diaminodiphenylsulfone.

The compound (B) is at least one member selected from the group consisting of dipentaerythritol pentaacrylate, dipentaerythritol hexaacrylate and polybasic acid-modified (meth) acryl oligomer.

The photopolymerization initiator (C) may be at least one selected from the group consisting of 1,2-octanedione-1- [4- (phenylthio) phenyl] -2- (O-benzoyloxime), ethanone, 1- [ (Methylbenzoyl) -9H-carbazol-3-yl] -, 1- (O-acetyloxime) and 1,2-propanedione- 1- [4- [4- (2-hydroxyethoxy) Phenyl] -2- (O-acetyloxime) in an amount of 50% by weight or more based on the total weight of the photopolymerization initiator.

The epoxy compound (D) can be obtained by reacting the epoxy compound (D) with 2- [4- (2,3-epoxypropoxy) phenyl] -2- [4- [ Phenyl] -1,3-bis [4- [1- [4- (2,3-epoxypropoxy) phenyl] -1- [4- [1- [4- Phenyl] -1-methylethyl] phenyl] ethyl] phenoxy] -2-propanol and 2- [4- (2,3-epoxypropoxy) Bis [4- (2,3-epoxypropoxy) phenyl] ethyl] phenyl] propane.

The photopolymerization initiator (C) is at least one selected from the group consisting of an? -Aminoalkylphenone-based, acylphosphine oxide-based, oxime ester-based photopolymerization initiator.

The additive (E) contains at least one kind of a coupling agent and a surfactant, and further, as a solvent, methyl 3-methoxypropionate and propylene glycol monomethyl ether acetate (hereinafter may be abbreviated as "PGMEA") And at least one member selected from the group consisting of

The photosensitive composition forms a cured film such as a protective film.

The cured film is used as a protective film of a color filter or in a display element or a solid-state image pickup element having a color filter.

The cured film is used as a transparent insulating film for a display element formed between a TFT and a transparent electrode or between a transparent electrode and an alignment film. Further, the cured film is used for an LED light-emitting body formed as a transparent protective film.

According to the above-described constitution, the photosensitive composition according to the present invention can be produced by reacting a polyester amide acid with a tetracarboxylic acid dianhydride, a diamine, a polyhydric hydroxy compound, and a monohydroxy compound in a predetermined ratio and composition to obtain a polyester amide acid The present invention can provide a cured film having excellent heat resistance, transparency and flatness as well as resolution and residual film ratio. Further, the cured film can be applied to various applications such as a color filter, a protective film, and an insulating film.

1. Photosensitive composition

The photosensitive composition according to the present invention is obtained by reacting a tetracarboxylic acid dianhydride, a diamine, a polyhydric hydroxy compound, and a monohydroxy compound as essential raw material components. (A) containing a polymerizable double bond, a compound (B) containing two or more polymerizable double bonds per one molecule other than the polyester amide acid (A), a photopolymerization initiator (C) , An epoxy compound (D) containing 2 to 10 epoxy groups per molecule and having a weight average molecular weight of less than 3,000, and an additive (E). The total amount of the compound (B) is 20 to 300 parts by weight and the total amount of the epoxy compound (D) is 20 to 200 parts by weight based on 100 parts by weight of the polyester amide acid (A).

In addition, the photosensitive composition according to the present invention may further contain other components than the above in the range in which the effect of the present invention can be obtained.

1-1. The polyester amide acid (A) having a polymerizable double bond

The polyester amide acid (A) is obtained by reacting a tetracarboxylic acid dianhydride, a diamine, a polyhydric hydroxy compound and a monohydroxy compound as essential raw material components. The polyester amide acid (A) is obtained by reacting X mole of tetracarboxylic acid dianhydride, Y mole of diamine and Z mole of polyhydric hydroxy compound at a ratio satisfying the relations of the above formulas (1) and (2) .

The polyester amide acid (A) has a structural unit represented by the formula (3), a structural unit represented by the formula (4), and a structural unit represented by the formula (5). In the formulas (3), (4) and (5), R ¹ is a residue obtained by removing two -CO-O-CO- from a tetracarboxylic acid dianhydride and R ² is a residue obtained by removing two -NH ₂ R ³ is a residue obtained by removing two -OH from a polyhydric hydroxy compound, and R ⁴ is a residue obtained by removing one -OH from a monohydroxy compound. At least one of R ³ and R ⁴ has a polymerizable double bond.

At least a solvent is required for the synthesis of the polyester amide acid (A). The solvent may be left as it is, and a liquid or gel-like photosensitive composition may be used in consideration of handleability and the like. In addition, the solvent may be removed to form a solid composition in consideration of transportability and the like.

The synthesis of the polyester amide acid (A) may contain a styrene-maleic anhydride copolymer as a raw material as necessary, and may contain other compounds than those mentioned above within the range not impairing the object of the present invention . Examples of other raw materials include silicon-containing monoamines.

1-1-1. Tetracarboxylic acid dianhydride

In the present invention, a tetracarboxylic acid dianhydride is used as a material for obtaining the polyester amide acid (A). Specific examples of the tetracarboxylic acid dianhydride include 3,3 ', 4,4'-diphenylether tetracarboxylic acid dianhydride (hereinafter may be abbreviated as ODPA in some cases), 1,2,3,4,4- Butane tetracarboxylic acid dianhydride (hereinafter may be abbreviated as BT-100), styrene-maleic anhydride copolymer (hereinafter abbreviated as SMA-1000P) have.

In addition to the above-mentioned tetracarboxylic acid dianhydrides, other tetracarboxylic acid dianhydrides such as 3,3 ', 4,4'-benzophenonetetracarboxylic dianhydride, 2,2', 3,3'-benzophenonetetracarboxylic dianhydride , 2,3,3 ', 4'-benzophenonetetracarboxylic acid dianhydride, 3,3', 4,4'-diphenylsulfone tetracarboxylic acid dianhydride, 2,2 ', 3,3'-diphenyl Sulfone tetracarboxylic acid dianhydride, 2,3,3 ', 4'-diphenylsulfone tetracarboxylic dianhydride, 3,3', 4,4'-diphenyl ether tetracarboxylic dianhydride, 2,2 ' 3,3'-diphenyl ether tetracarboxylic acid dianhydride, 2,2- [bis (3,4-dicarboxyphenyl)] hexa Fluorobutane tetracarboxylic acid dianhydride, methylcyclobutane tetracarboxylic acid dianhydride, cyclohexane tetracarboxylic acid dianhydride, methylcyclobutane tetracarboxylic acid dianhydride, cyclohexanedicarboxylic acid dianhydride, Pentane tetracarboxylic acid there may be mentioned anhydrides, cyclohexane tetracarboxylic dianhydride, ethane tetracarboxylic dianhydride, and butane tetracarboxylic acid dianhydride, the acid wherein the tetracarboxylic acid can be used at least one kind of anhydride.

Among these, acid anhydrides which give good transparency to the cured film are 3,3 ', 4,4'-diphenylsulfone tetracarboxylic acid dianhydride, 3,3', 4,4'-diphenyl ether tetracarboxylic acid 1,2,3,4-butanetetracarboxylic acid dianhydride, and TMEG-100 are more preferable, and 3, 4-dicarboxylic acid dianhydride, , 3 ', 4,4'-diphenyl ether tetracarboxylic acid dianhydride, 3,3', 4,4'-diphenylsulfonetetracarboxylic dianhydride and 1,2,3,4-butanetetracarboxylic acid Anhydrides are particularly preferred.

1-1-2. Diamine

In the present invention, a diamine is used as a material for obtaining the polyester amide acid (A). Specific examples of diamines include 3,3'-diaminodiphenylsulfone (hereinafter abbreviated as DDS in some cases) used in Examples.

Specific examples of the diamines include, in addition to those described above, 4,4'-diaminodiphenylsulfone, 3,4'-diaminodiphenylsulfone, bis [4- (4-aminophenoxy) phenyl] sulfone (4-aminophenoxy) phenyl] sulfone, bis [4- (3-aminophenoxy) phenyl] sulfone, bis [3- Phenyl) sulfone, and 2,2-bis [4- (4-aminophenoxy) phenyl] ] Hexafluoropropane, and at least one of the above diamines can be used.

Of these, diamines which give good transparency to the cured film are more preferably 3,3'-diaminodiphenylsulfone and bis [4- (3-aminophenoxy) phenyl] sulfone, Diphenyl sulfone is particularly preferred.

1-1-3. The polyhydric hydroxy compound

The present invention uses a polyhydric hydroxy compound having no polymerizable double bond and / or a polyhydric hydroxy compound having a polymerizable double bond as a material for obtaining a polyester amide acid. Specific examples of the polyhydric hydroxy compound are preferably 1,4-butanediol, epoxy ester 70PA (trade name, manufactured by Kyoeisha Chemical Co., Ltd.), epoxy ester 80MFA (trade name, manufactured by Kyoeisha Chemical Co., Ltd.) Ester 3002A (N) (trade name, manufactured by Kyoeisha Chemical Co., Ltd.).

As the polyhydric hydroxy compound having no polymerizable double bond, ethylene glycol, diethylene glycol, triethylene glycol, tetraethylene glycol, polyethylene glycol having a weight average molecular weight of 1,000 or less, propylene glycol, dipropylene glycol, tripropylene glycol, Tetrapropylene glycol, polypropylene glycol having a weight average molecular weight of 1,000 or less, 1,2-butanediol, 1,3-butanediol, 1,2-pentanediol, 1,5-pentanediol, , Pentanediol, 1,2-hexanediol, 1,6-hexanediol, 2,5-hexanediol, 1,2,6-hexanetriol, 1,2-heptanediol, 1,7- Diol, 1,2,7-heptanetriol, 1,2-octanediol, 1,8-octanediol, 3,6-octanediol, 1,2,8-octanetriol, 1,9-nonanediol, 1,2,9-nonanthiol, 1,2-decanediol, 1,10-decanediol, 1,2,10-decanetriol, 1,2-dodecanediol, , 12-dodecanediol, glycerin, trimethylol propane, pentaerythritol, dipentaerythritol Bis (2-hydroxyphenyl) propane), bisphenol S (bis (4-hydroxyphenyl) sulfone), bisphenol F (bis (4-hydroxyphenyl) methane), 2,2-bis (4-hydroxycyclohexyl) propane, 4,4'-dihydroxydicyclohexyl, 2-hydroxybenzyl alcohol, 4-hydroxybenzyl alcohol , 2- (4-hydroxyphenyl) ethanol, diethanolamine and triethanolamine.

Among them, the compound having good solubility in a reaction solvent is preferably at least one compound selected from the group consisting of ethylene glycol, propylene glycol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, (2-hydroxyethyl), 2,2-bis (4-hydroxycyclohexyl) propane, 4,4'-dihydroxydicyclohexyl, 2-hydroxybenzyl alcohol, 4- Hydroxybenzyl alcohol, and 2- (4-hydroxyphenyl) ethanol are more preferable. Particularly preferred are 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, 2-hydroxybenzyl alcohol, 4-hydroxybenzyl alcohol and 2- (4-hydroxyphenyl) .

On the other hand, as specific examples of the polyhydric hydroxy compound having a polymerizable double bond, glycerin monoallyl ether, trimethylolpropane monoallyl ether, pentaerythritol monoallyl ether, pentaerythritol diallyl ether, dipentaerythritol Monoallyl ether, dipentaerythritol diallyl ether, dipentaerythritol triallyl ether, dipentaerythritol tetralyl ether, sorbitol monoallyl ether, sorbitol diallyl ether, sorbitol triallyl ether, sorbitol tetraallyl ether, glycerol mono (Meth) acrylate, dipentaerythritol mono (meth) acrylate, dipentaerythritol mono (meth) acrylate, pentaerythritol mono (meth) acrylate, (Meth) acrylate, dipentaerythritol tri (meth) acrylate, dipentaerythritol (Meth) acrylate, sorbitol tetra (meth) acrylate, sorbitol mono (meth) acrylate, sorbitol di (meth) acrylate, sorbitol tri (Meth) acrylic acid modified product of propylene glycol diglycidyl ether, a (meth) acrylic acid modified product of tripropylene glycol diglycidyl ether, a (meth) acrylic acid modified product of glycerin diglycidyl ether , (Meth) acrylic acid modified products of bisphenol A diglycidyl ether, (meth) acrylic acid modified products of propylene oxide modified bisphenol A diglycidyl ether, (meth) acrylic acid modified products of bisphenol S diglycidyl ether, (Meth) acrylic acid modified product of bisphenol S diglycidyl ether, (meth) acrylic acid modified product of bisphenol F diglycidyl ether, (Meth) acrylic acid modified product of bisphenol F diglycidyl ether, (meth) acrylic acid modified product of non-diylolediglycidyl ether, (meth) acrylic acid modified product of biphenol diglycidyl ether, fluorene di (Meth) acrylic acid modified product of phenol diglycidyl ether, (meth) acrylic acid modified product of cyclohexane-1,4-dimethanol diglycidyl ether, (meth) acrylic acid modified product of hydrogenated bisphenol A diglycidyl ether (Meth) acrylic acid modified product of water, tricyclodecane dimethanol diglycidyl ether, and (meth) acrylic acid modified product of another compound containing two or more epoxy groups per molecule, and at least one Can be used.

Of these, compounds having good solubility in a reaction solvent include (meth) acrylic acid modified products of ethylene glycol diglycidyl ether, (meth) acrylic acid modified products of propylene glycol diglycidyl ether, and (meth) acrylic acid modified products of glycerin diglycidyl ether Acrylic acid modified product of bisphenol A diglycidyl ether, (meth) acrylic acid modified product of bisphenol A diglycidyl ether, (meth) acrylic acid modified product of bisphenol A diglycidyl ether, (meth) acrylic acid modified product of bisphenol A diglycidyl ether, (Meth) acrylic acid modified product of propylene oxide modified bisphenol S diglycidyl ether, (meth) acrylic acid modified product of bisphenol F diglycidyl ether, and (meth) acrylic acid modified product of propylene oxide modified bisphenol F diglycidyl ether Methacrylic acid modified product is more preferable. Examples of the (meth) acrylic acid modified product of ethylene glycol diglycidyl ether, the (meth) acrylic acid modified product of propylene glycol diglycidyl ether, the (meth) acrylic acid modified product of tripropylene glycol diglycidyl ether, (Meth) acrylic acid modified product of glycidyl ether, (meth) acrylic acid modified product of bisphenol A diglycidyl ether, and (meth) acrylic acid modified product of propylene oxide modified bisphenol A diglycidyl ether are particularly preferable.

Methacrylic acid modified product of ethylene glycol diglycidyl ether, acrylic acid modified product of propylene glycol diglycidyl ether, acrylic acid modified product of tripropylene glycol diglycidyl ether, acrylic acid modified product of glycerin diglycidyl ether, Methacrylic acid modified products of bisphenol A diglycidyl ether, acrylic acid modified products of bisphenol A diglycidyl ether, methacrylic acid modified products of propylene oxide modified bisphenol A diglycidyl ether, and propylene oxide modified bisphenol A di As acrylic acid-modified products of glycidyl ether, the following commercially available products can be used.

Specifically, a specific example of the methacrylic acid-modified product of ethylene glycol diglycidyl ether is epoxy ester 40EM (trade name, manufactured by Kyoeisha Chemical Co., Ltd.). A concrete example of the acrylic acid-modified product of propylene glycol diglycidyl ether is epoxy ester 70PA (trade name, manufactured by Kyoeisha Chemical Co., Ltd.). A concrete example of the acrylic acid-modified product of tripropylene glycol diglycidyl ether is epoxy ester 200PA (trade name, manufactured by Kyoeisha Chemical Co., Ltd.). A concrete example of an acrylic acid-modified product of glycerin diglycidyl ether is an epoxy ester 80 MFA (trade name, manufactured by Kyoeisha Chemical Co., Ltd.). A specific example of the methacrylic acid-modified product of bisphenol A diglycidyl ether is epoxy ester 3000MK (trade name, manufactured by Kyoeisha Chemical Co., Ltd.). A specific example of the acrylic acid-modified product of bisphenol A diglycidyl ether is epoxy ester 3000A (trade name, manufactured by Kyoeisha Chemical Co., Ltd.). A specific example of the methacrylic acid-modified product of propylene oxide-modified bisphenol A diglycidyl ether is epoxy ester 3002M (N) (trade name, manufactured by Kyoeisha Chemical Co., Ltd.). A concrete example of the acrylic acid-modified product of propylene oxide-modified bisphenol A diglycidyl ether is epoxy ester 3002A (N) (trade name, manufactured by Kyoeisha Chemical Co., Ltd.).

1-1-4. Monohydroxy compound

In the present invention, as a material for obtaining the polyester amide acid (A), a monohydroxy compound having no polymerizable double bond and / or a monohydroxy compound having a polymerizable double bond are used.

As specific examples of the monohydroxy compound, benzyl alcohol, 2-hydroxyethyl methacrylate, 4-hydroxybutyl acrylate, 4-hydroxyphenyl methacrylate, 1,4-cyclo Hexane dimethanol monoacrylate (hereinafter may be abbreviated as CHDMMA) (trade name, manufactured by Nippon Hoso K.K.).

When the monohydroxy compound is used, the storage stability of the photosensitive composition is improved.

Concrete examples of the monohydroxy compound having no polymerizable double bond are preferably isopropyl alcohol, benzyl alcohol, propylene glycol monoethyl ether, propylene glycol monomethyl ether, dipropylene glycol monoethyl ether, dipropylene glycol monomethyl Ether, ethylene glycol monoethyl ether, ethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monomethyl ether, terpineol, 3-ethyl-3-hydroxymethyloxetane and dimethylbenzylcarbinol .

Of these, benzyl alcohol, propylene glycol monoethyl ether and 3-ethyl-3-hydroxymethyloxetane are more preferable. Taking into account the compatibility when the polyester amide acid (A) made by using these is mixed with the epoxy group-containing polymer, the epoxy compound (D) and the epoxy curing agent, and the coating property of the photosensitive composition on the color filter, The use of a benzyl alcohol is particularly preferable for the monohydroxy compound having no bond.

Specific examples of the monohydroxy compound having a polymerizable double bond are preferably furfuryl alcohol, allyl alcohol, hydroxyethyl (meth) acrylate, hydroxypropyl (meth) acrylate, hydroxybutyl Hydroxypropyl (meth) acrylate, 4-hydroxyphenyl (meth) acrylate, p-hydroxy (meth) acrylanilide, 1,4-cyclohexanedimethanol mono Acrylate, trimethylolpropane di (meth) acrylate, pentaerythritol tri (meth) acrylate, dipentaerythritol penta (meth) acrylate, 3- (2-hydroxyphenyl) (Meta) acrylic acid modified product of t-butylphenyl glycidyl ether, and another compound containing one epoxy group per molecule (meth) acrylate, a (meth) acrylic acid modified product of phenylglycidyl ether, ) Acrylic acid denatured water And it can be used at least one of them.

Among these, hydroxyethyl (meth) acrylate, hydroxypropyl (meth) acrylate, hydroxybutyl (meth) acrylate, 2-hydroxy-3-phenoxypropyl (meth) (Meth) acrylic anilide, 1,4-cyclohexanedimethanol mono (meth) acrylate, and 3- (2-hydroxyphenyl) methacrylate are more preferable. Taking into account the compatibility when the polyester amide acid (A) made by using these is mixed with the epoxy group-containing polymer, the epoxy compound (D) and the epoxy curing agent, and the coating property of the photosensitive composition on the color filter, (Meth) acrylate, hydroxypropyl (meth) acrylate, hydroxybutyl (meth) acrylate, 4-hydroxyphenyl (meth) acrylate, p-hydroxy (Meth) acryl anilide, and 1,4-cyclohexanedimethanol mono (meth) acrylate are particularly preferable.

As the 4-hydroxyphenyl methacrylate, p-hydroxymethacrylanilide and 1,4-cyclohexanedimethanol monoacrylate, the following commercially available products can be used. A specific example of 4-hydroxyphenyl methacrylate is HQMA (trade name; manufactured by Osaka Organic Chemical Industry Co., Ltd.). A specific example of p-hydroxymethacrylanilide is HMAd (trade name, Osaka Organic Chemical Industry Co., Ltd.). A specific example of 1,4-cyclohexanedimethanol monoacrylate is 1,4-cyclohexanedimethanol monoacrylate (CHDMMA) (trade name, manufactured by NIPPON PHASE CORPORATION).

The monohydroxy compound is preferably reacted in an amount of 0 to 300 parts by weight per 100 parts by weight of the total amount of the tetracarboxylic acid anhydride, diamine and polyhydric hydroxy compound. More preferably 5 to 200 parts by weight.

1-1-5. Styrene-maleic anhydride copolymer

The polyester amide acid used in the present invention may be synthesized by using a compound having three or more acid anhydride groups in the raw material. This is preferable because transparency of the cured film is improved. Examples of the compound having three or more acid anhydride groups include a styrene-maleic anhydride copolymer. When a polyester amide acid is synthesized by using a styrene-maleic anhydride copolymer as a raw material, the sum of the molar number of the tetracarboxylic acid dianhydride and the mole number of the styrene-maleic anhydride copolymer is referred to as " X ". The molar ratio of styrene / maleic anhydride to styrene / maleic anhydride copolymer is 0.5 to 4, preferably 1 to 3. Further, 1 or 2 is more preferable, and 1 is particularly preferable.

Specific examples of the styrene-maleic anhydride copolymer include SMA3000P, SMA2000P, and SMA1000P (all trade names, Kawahara Oil Company). Of these, SMA1000P, which is excellent in the heat resistance and alkali resistance of the cured film, is particularly preferable.

1-1-6. Silicon-containing monoamines

The synthesis of the polyester amide acid may include raw materials other than those described above as necessary insofar as the object of the present invention is not impaired, and examples of other raw materials include silicon-containing monoamines.

Specific examples of the silicon-containing monoamines used in the present invention are preferably 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-aminopropylmethyldimethoxysilane, 3- Aminobutyltrimethoxysilane, p-aminophenyltriethoxysilane, p-aminophenyltriethoxysilane, p-aminophenyltrimethoxysilane, p-aminobutyltrimethoxysilane, Aminophenylmethyldimethoxysilane, p-aminophenylmethyldiethoxysilane, m-aminophenyltrimethoxysilane, and m-aminophenylmethyldiethoxysilane. At least one of them may be used.

Of these, 3-aminopropyltriethoxysilane and p-aminophenyltrimethoxysilane which are excellent in the acid resistance of the cured film are more preferable, and 3-aminopropyltriethoxysilane is particularly preferable in view of acid resistance and compatibility.

The silicon-containing monoamine preferably contains 0 to 300 parts by weight, more preferably 5 to 200 parts by weight, per 100 parts by weight of the total amount of the tetracarboxylic acid anhydride, diamine and polyhydric hydroxy compound.

1-1-7. Solvent used for synthesis reaction of polyester amide acid

Specific examples of the solvent used in the synthesis reaction for obtaining the polyester amide acid include diethylene glycol dimethyl ether, diethylene glycol methyl ethyl ether, diethylene glycol diethyl ether, diethylene glycol monoethyl ether acetate, ethylene glycol monoethyl Ether acetate, propylene glycol monomethyl ether acetate, methyl 3-methoxypropionate, ethyl 3-ethoxypropionate, ethyl lactate, and cyclohexanone. Of these, propylene glycol monomethyl ether acetate, methyl 3-methoxypropionate, or diethylene glycol methyl ethyl ether are preferable.

1-1-8. Synthesis method of polyester amide acid

The method for synthesizing polyester amide acid used in the present invention is to react X-mole of tetracarboxylic acid dianhydride, Y-diamine, Z-mole polyhydric hydroxy compound and monohydroxy compound in the solvent. At this time, it is preferable that X, Y, and Z are determined by the ratio in which the relationship of the above-mentioned formula (1) and the formula (2) is satisfied therebetween. Within this range, the solubility of the polyester amide acid in the solvent is high, and the applicability of the composition is improved. As a result, a cured film excellent in flatness can be obtained.

In the formula (1), preferably 0.7? Z / Y? 7.0, more preferably 1.0? Z / Y? 5.0. In the formula (2), 0.5? (Y + Z) / X? 4.0, and more preferably 0.6? Y + Z / X? 2.0.

In the synthesis of the polyester amide acid, an acid anhydride group (-CO-O-CO (-CO-O-CO)) is added at the terminal under the condition that X is excessively used for Y + Z within the range of the formula (2) without using a monohydroxy compound. -) is thought to be generated excessively at a terminal end than a molecule having an amino group or hydroxyl group. On the other hand, when a monohydroxy compound is added in the reaction of such a monomer composition, the terminal can be esterified by reacting with an acid anhydride group at the molecular end. Since the polyester amide acid used in the present invention is obtained by reacting with a monohydroxy compound added thereto, the compatibility of the epoxy compound and the epoxy curing agent is improved and the coating property of the photosensitive composition is improved.

In the case of reacting with the above-described monomer composition, a silicon-containing monoamine may be added in order to react with an acid anhydride group at the terminal of the molecule to introduce a silyl group at the terminal. When a photosensitive composition containing a polyester amide acid obtained by adding and reacting a silicon-containing monoamine is used, the acid resistance of the cured film is improved.

When the reaction solvent is used in an amount of 100 parts by weight or more based on 100 parts by weight of the total amount of the tetracarboxylic acid anhydride, diamine and polyhydric hydroxy compound, the reaction is preferable because the reaction proceeds smoothly. The reaction is preferably carried out at 40 ° C to 200 ° C for 0.2 to 20 hours.

The order of addition of the raw materials to the reaction system is not particularly limited. That is, a method in which a tetracarboxylic acid dianhydride, a diamine and a polyhydric hydroxy compound are simultaneously added to a reaction solvent, a method in which a tetracarboxylic acid dianhydride is added after dissolving a diamine and a polyhydric hydroxy compound in a reaction solvent, A method of previously reacting an acid anhydride and a polyhydric hydroxy compound and then adding a diamine to the reaction product or a method of reacting a tetracarboxylic acid dianhydride with a diamine in advance and then adding a polyhydroxy compound to the reaction product Either method can be used. The monohydroxy compound may be added at any point in the reaction.

When the above-mentioned silicon-containing monoamine is reacted, after the reaction of the tetracarboxylic acid dianhydride with the diamine and the polyhydric hydroxy compound, the reaction solution is cooled to 40 ° C or lower, the silicon-containing monoamine is added, For 0.1 to 6 hours. The monohydroxy compound may be added at any point in the reaction.

The polyester amide thus synthesized contains a structural unit represented by the formula (3), a structural unit represented by the formula (4) and a structural unit represented by the formula (5), and the terminal thereof is a tetracarboxylic acid anhydride , A diamine, a polyhydric hydroxy compound, or an acid anhydride group derived from a monohydroxy compound, an amino group, a hydroxyl group, a monovalent organic group, or an additive other than these compounds. By including such a constitution, the curability is improved.

The weight average molecular weight of the resulting polyester amide acid is preferably 1,000 to 200,000, more preferably 3,000 to 50,000. Within these ranges, flatness and heat resistance are good.

The weight average molecular weight in the present specification is a value in terms of polystyrene determined by the GPC method (column temperature: 35 캜, flow rate: 1 ml / min). PLgel MIXED-D (Agilent Technologies, Inc.) was used as a column, and THF was used as a mobile phase. The column was made of polystyrene having a molecular weight of 645 to 132,900 (for example, polystyrene calibration kit PL2010-0102 manufactured by Agilent Technologies Co., . The weight average molecular weights of commercially available products in this specification are catalog published values.

1-2. The compound (B) having a polymerizable double bond

1-2-1. A compound having two or more polymerizable double bonds per molecule

The compound having a polymerizable double bond used in the present invention is not particularly limited, but a compound having two or more polymerizable double bonds per molecule is preferable.

When the compound having a polymerizable double bond is contained in an amount of 50 to 300 parts by weight based on 100 parts by weight of the polyester amide acid (A), the residual film ratio after development becomes good.

Examples of the compound having two or more polymerizable double bonds per molecule contained in the photosensitive composition of the present invention include ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, triethylene glycol di Acrylate, epichlorohydrin denatured ethylene glycol di (meth) acrylate, epichlorohydrin denatured diethylene glycol di (meth) acrylate, polyethylene glycol di (meth) acrylate, Epichlorohydrin modified diethylene glycol di (meth) acrylate, epichlorohydrin modified tetraethylene glycol di (meth) acrylate, epichlorohydrin modified polyethylene glycol di (meth) acrylate, propylene glycol di (meth) Acrylate, dipropylene glycol di (meth) acrylate, tripropylene glycol di (meth) acrylate, tetrapropylene glycol di Propylene glycol di (meth) acrylate, epichlorohydrin-modified dipropylene glycol di (meth) acrylate, epichlorohydrin-modified propylene glycol di (meth) (Meth) acrylate, epichlorohydrin-modified polypropylene glycol di (meth) acrylate, trimethylolpropane tri (meth) acrylate, epichlorohydrin-modified polypropylene glycol di (Meth) acrylate, ethylene oxide modified trimethylol propane tri (meth) acrylate, propylene oxide modified trimethylol propane tri (meth) acrylate, epichlorohydrin modified trimethylol propane tri (meth) acrylate, ditrimethylol propane tetra (Meth) acrylate, glycerol (meth) acrylate, glycerol di Acrylate, epichlorohydrin-modified glycerol tri (meth) acrylate, 1,6-hexanediol di (meth) acrylate, epichlorohydrin-modified 1,6-hexanediol di (Meth) acrylate, methoxylated cyclohexyldi (meth) acrylate, neopentyl glycol di (meth) acrylate, hydroxypivalic neopentyl glycol di (meth) acrylate, caprolactone-modified hydroxypivalic acid neopentyl (Meth) acrylate, pentaerythritol tetra (meth) acrylate, diglycerin tetra (meth) acrylate, diglycerin ethylene oxide modified acrylate, pentaerythritol tri (Meth) acrylate, dipentaerythritol penta (meth) acrylate, alkyl-modified dipentaerythritol penta (meth) acrylate, alkyl modified (Meth) acrylate, dipentaerythritol tetra (meth) acrylate, alkyl modified dipentaerythritol tri (meth) acrylate, dipentaerythritol hexa (meth) acrylate, caprolactone modified dipentaerythritol hexa (Meth) acrylate, di (meth) acrylate oligomer, allylated cyclohexyl di (meth) acrylate, bis [(meth) acryloxyneopentyl glycol] adipate, bisphenol A di (meth) acrylate, ethylene oxide modified bisphenol A di (Meth) acrylate, ethylene oxide modified bisphenol F di (meth) acrylate, ethylene oxide modified bisphenol F di (meth) acrylate, bisphenol F di Di (meth) acrylate, 1,3-butylene glycol (meth) acrylate, dicyclopentanyl diacrylate, polyester diacrylate, poly (Meth) acrylate modified with ethylene oxide, tri (meth) acrylate modified with ethylene oxide, epichlorohydrin (meth) acrylate modified with ethylene oxide, polyester tetraacrylate, polyester pentaacrylate, polyester hexaacrylate, ethylene oxide modified di (Meth) acrylate modified with trimethylolpropane di (meth) acrylate, tetrabromobisphenol A di (meth) acrylate, triglycerol di (meth) acrylate, neopentyl glycol modified trimethylolpropane di Diacrylate, isocyanuric acid ethylene oxide modified triacrylate, caprolactone modified tris [(meth) acryloxyethyl] isocyanurate, (meth) acryl isocyanurate, phenylglycidyl ether acrylate hexamethylene diisocyanate Urethane prepolymer, phenylglycidyl ether arc Pentaerythritol triacrylate hexamethylene diisocyanate urethane prepolymer, pentaerythritol triacrylate toluene diisocyanate urethane prepolymer, pentaerythritol triacrylate isophorone diisocyanate urethane prepolymer, dipentaerythritol pentaerythritol triacrylate, pentaerythritol triacrylate, (Meth) acrylic acid modified product of a phenol novolak type epoxy resin, a (meth) acrylic acid modified product of a cresol novolak type epoxy resin, and a carboxylic acid (meth) acrylic acid modified product of a cresol novolak type epoxy resin. Containing urethane acrylate oligomer and the like.

The compound having two or more polymerizable double bonds per molecule may be used alone or in combination of two or more.

Among the compounds having two or more polymerizable double bonds per molecule, it is preferable to use at least one compound selected from the group consisting of trimethylolpropane triacrylate, pentaerythritol triacrylate, pentaerythritol tetraacrylate, dipentaerythritol pentaacrylate, dipentaerythritol hexaacryl It is preferable to use polybasic acid-modified (meth) acryl oligomer, isocyanuric acid ethylene oxide-modified diacrylate, isocyanuric acid ethylene oxide-modified triacrylate, or a mixture thereof in view of heat resistance and chemical resistance of the cured film.

Trimethylolpropane triacrylate, pentaerythritol triacrylate, pentaerythritol tetraacrylate, dipentaerythritol pentaacrylate, dipentaerythritol hexaacrylate, polybasic acid modified (meth) acryl oligomer, isocyanuric acid ethylene oxide As the modified diacrylate, isocyanuric acid ethylene oxide modified triacrylate, or a mixture thereof, the following commercially available products can be used.

A specific example of trimethylolpropane triacrylate is Aronix M-309 (trade name, manufactured by Toa Synthetic Co., Ltd.). Specific examples of mixtures of pentaerythritol triacrylate and pentaerythritol tetraacrylate include Aronix M-306 (65-70 wt%), M-305 (55-63 wt%), M-303 M-450 (25 to 40% by weight) and M-450 (less than 10% by weight, hereinafter sometimes abbreviated as "M-450" And the content is the catalog value of the content of pentaerythritol triacrylate in the mixture). Specific examples of mixtures of dipentaerythritol pentaacrylate and dipentaerythritol hexaacrylate include Aronix M-403 (50-60 wt%), M-400 (40-50 wt%), M-402 M-404 (30 to 40% by weight), M-406 (25 to 35% by weight), and M-405 (10 to 20% % By weight) (all trade names: Doa Synthetic Co., Ltd., content in parentheses is the catalog value of the content of dipentaerythritol pentaacrylate in the mixture). Concrete examples of the polybasic acid-modified (meth) acryl oligomer include Aronix M-510 and M-520 (all trade names, Doa Synthetic Co., Ltd.). A specific example of isocyanuric acid ethylene oxide-modified diacrylate is ARONIX M-215 (trade name, manufactured by Toa Gosei Co., Ltd.). Specific examples of the mixture of isocyanuric acid ethylene oxide-modified diacrylate and isocyanuric acid ethylene oxide-modified triacrylate include Aronix M-313 (30 to 40 wt%) and M-315 (3 to 13 wt% Quot; M-315 ") (all trade names, Doa Synthetic Co., Ltd., content in parentheses is the catalog value of the content of isocyanuric acid ethylene oxide-modified diacrylate in the mixture). A specific example of the acrylic acid-modified product of the phenol novolak type epoxy resin is TEA-100 (trade name, manufactured by KSM). A specific example of the acrylic acid-modified product of the cresol novolak type epoxy resin is CNEA-100 (trade name, KSM Co., Ltd.).

1-2-2. A compound having at least one polymerizable double bond per molecule and at least one functional group selected from -OH and -COOH

From the viewpoint of resolution, the photosensitive composition of the present invention may further contain a compound having one polymerizable double bond per molecule and at least one functional group selected from -OH and -COOH. The compound having one polymerizable double bond per molecule and having at least one functional group selected from -OH and -COOH per molecule is preferably used in an amount of 1 to 50 parts by weight per 100 parts by weight of the polyester amide acid (A) The resolution is improved.

Examples of the compound having one such polymerizable double bond per molecule and having at least one functional group of -OH and -COOH per one molecule include (meth) acrylic acid, hydroxyethyl (meth) acrylate Acrylate, hydroxypropyl (meth) acrylate, hydroxybutyl (meth) acrylate, 2-hydroxy-3-phenoxypropyl (meth) acrylate, 2- (meth) acryloyloxyethyl succinate, (Meth) acryloyloxyethyl methacrylate, 2- (meth) acryloyloxyethyl phthalate, 2- (meth) acryloyloxyethyl phthalate, 2- (Meth) acrylate, 4-hydroxybutyl (meth) acrylate, 1,4-cyclohexanedimethanol mono (meth) acrylate, hydroxyethyl (meth) acrylate, glycerin mono (Meth) acrylate, 3- (2-hydroxyphenyl) acrylic acid, and? -Carboxyethyl It can be the root.

Among them, (meth) acrylic acid 4-hydroxyphenyl and p-hydroxy (meth) acrylanilide have good resolution.

1-3. The photopolymerization initiator (C)

The photopolymerization initiator contained in the photosensitive composition of the present invention can initiate polymerization of a composition containing a polyester amide acid (A), a compound (B), a photopolymerization initiator (C), an epoxy compound (D) and an additive (E) It is not particularly limited.

Examples of the photopolymerization initiator contained in the photosensitive composition of the present invention include benzophenone, Michler's ketone, 4,4'-bis (diethylamino) benzophenone, xanthone, thioxanthone, isopropylxanthone, Diethylthioxanthone, 2-ethyl anthraquinone, acetophenone, 2-hydroxy-2-methylpropiophenone, 2-hydroxy-2-methyl-4'-isopropylpropiophenone, 1-hydroxycyclo Hexyl phenyl ketone, isopropyl benzoin ether, isobutyl benzoin ether, 2,2-diethoxy acetophenone, 2,2-dimethoxy-2-phenylacetophenone, camphorquinone, benzanthrone, (4-methylthio) phenyl] -2-morpholinopropane-1-one (trade name; IRGACURE 907, BASF Japan KK) 4-dimethyl-aminobenzoic acid isoamyl, 4,4'-di (t-butyldimethylsilyl) aminobenzoate, Butyl peroxycarbonyl) (T-butylperoxycarbonyl) benzophenone, 1,2-octanedione-1- [4- (phenylthio) phenyl] -2- (O- benzoyloxime) (1-ethyl-6- (2-methylbenzoyl) -9H-carbazol-3-yl] -, 1- (O- Propyldion-1- [4- [4- (2-hydroxyethoxy) phenylthio] propionate (trade name: IRGACURE OXE02, BASF Japan KK), IRGACURE OXE03 Phenyl] -2- (O-acetyloxime) (for example, trade name: Adekaacruz NCI-930, ADEKA Co., Ltd.), Adekaacruz NCI-831 (trade name, ADEKA Co., Trimethylbenzoyldiphenylphosphine oxide, 2- (4'-methoxystyryl) -4,6-bis (trichloromethyl) -s-triazine, 4,6-bis (trichloromethyl) -s-triazine, 2- (2 ', 4'-dimethoxystyryl) -4,6- Bis (trichloromethyl) -s-t- Azine, 2- (2'-methoxystyryl) -4,6-bis (trichloromethyl) -s-triazine, 2- (4'-pentyloxystyryl) -4,6- Methyl) -s-triazine, 4- [pN, N-di (ethoxycarbonylmethyl)] -2,6-di (trichloromethyl) (2'-chlorophenyl) -s-triazine, 1,3-bis (trichloromethyl) -5- (4'-methoxyphenyl) Aminostyryl) benzoxazole, 2- (p-dimethylaminostyryl) benzothiazole, 2-mercaptobenzothiazole, 3,3'-carbonylbis chlorophenyl) -4,4 ', 5,5'-tetraphenyl-1,2'-biimidazole, 2,2'-bis (2-chlorophenyl) -Tetrakis (4-ethoxycarbonylphenyl) -1,2'-biimidazole, 2,2'-bis (2,4-dichlorophenyl) -4,4 ', 5,5'- (2,4-dibromophenyl) -4,4 ', 5,5'-tetraphenyl-1,2'-biimidazole, 2,2'-bis 2'-bis (2,4,6-tri Chlorophenyl) -4,4 ', 5,5'-tetraphenyl-1,2'-biimidazole, 3- (2-methyl-2-dimethylaminopropionyl) carbazole, 3,6-bis -methyl-2-morpholino-propionyl) -9-n- dodecyl carbazole, 1-hydroxycyclohexyl phenyl ketone, and bis (η ⁵ -2,4- cyclopentadiene-1-yl) -bis (2,6-difluoro-3- (1H-pyrrol-1-yl) -phenyl) titanium.

The photopolymerization initiator may be used alone, or two or more photopolymerization initiators may be used in combination. Of the photopolymerization initiators, α-aminoalkylphenone-based, acylphosphine oxide-based, and oximeester-based photopolymerization initiators are preferred from the viewpoints of coating sensitivity at the time of exposure and transparency of the cured film. Here, in the present specification, a thin film obtained by preliminarily drying (prebaking) a thin film of a photosensitive composition formed on a substrate by spin coating, printing, or other methods is referred to as a " coating film ". This coating film is subjected to a subsequent process such as exposure-development-cleaning-drying, and then becomes a cured film by main firing (post-baking). In the present specification, the thin films in the steps from the preliminary drying to the drying are all referred to as " coating films ", and at any step of the film formation step, for example, Of the coating film.

Among the photopolymerization initiators, 1,2-octanedione-1- [4- (phenylthio) phenyl] -2- (O-benzoyloxime) Hydroxyethoxy) phenylthio] phenyl] -2- (O-acetyloxime) is preferably 20% by weight or more based on the total weight of the photopolymerization initiator from the viewpoints of sensitivity of the coating film and transparency of the cured film. It is more preferable that the content is 50% by weight or more. Wherein the photopolymerization initiator is at least one selected from the group consisting of 1,2-octanedione-1- [4- (phenylthio) phenyl] -2- (O-benzoyloxime) Phenylthio] phenyl] -2- (O-acetyloxime) may be used.

1-4. The epoxy compound (D)

The epoxy compound (D) used in the present invention contains 2 to 10 epoxy groups per molecule and has a weight average molecular weight of less than 3,000. By adding the epoxy compound (D) to the photosensitive composition of the present invention, the heat resistance of the cured film can be enhanced. When the epoxy compound (D) is 20 to 150 parts by weight based on 100 parts by weight of the polyester amide acid (A), the flatness is improved.

As a preferable example of the epoxy compound, 3 ', 4'-epoxycyclohexylmethyl-3,4-epoxycyclohexanecarboxylate (for example, trade name: Celloxide 2021P, Daicel Inc.) (2-methyloxylanyl) -7-oxabicyclo [4.1.0] heptane (trade name; Celloxide 3000, Daicel Corporation), 2- [4- (2,3-epoxypropoxy) phenyl Bis [4- [1- [4- (2, 3-epoxypropoxy) phenyl] ethyl] Phenoxy] phenyl] -1-methylethyl] phenyl] ethyl] phenoxy] -2-propanol Phenyl] ethyl] phenyl] propane (for example, 2- [4- 1,1,1-tris (4-hydroxyphenyl) ethane triglycidyl ether (for example, trade name: JER 1032H60, manufactured by Mitsubishi Chemical Corporation), 1,3- Bis (oxiranyl meth (1H, 3H, 5H) -triene, 2,2-bis (hydroxymethyl) -1-butanol (Product name: EHPE3150, Daicel), jER 828, 1004, 1009 (all trade names, manufactured by Mitsubishi Chemical Corporation), jER YX4000 , YX4000H, YL6121H (all trade names, manufactured by Mitsubishi Chemical Corporation), NC-3000, NC-3000-L, NC-3000-H and NC-3100 (all trade names; Nippon Yakusho Co., Ltd.).

1-5. The ratio of the polyester amide acid (A), the compound (B), the photopolymerization initiator (C) and the epoxy compound (D)

In the photosensitive composition of the present invention, the ratio of the compound (B) to the polyester amide acid (A) is 20 to 300 parts by weight based on 100 parts by weight of the polyester amide acid (A). When the ratio of the compound (B) is within this range, the balance of heat resistance, flatness, chemical resistance and residual film ratio after development is good. It is more preferable that the amount of the compound (B) is in the range of 100 to 300 parts by weight.

In the photosensitive composition of the present invention, the proportion of the epoxy compound (D) is 20 to 200 parts by weight based on 100 parts by weight of the polyester amide acid (A). When the ratio of the epoxy compound (D) is within this range, the balance between heat resistance and flatness is good. It is more preferable that the epoxy compound (D) is in the range of 20 to 150 parts by weight.

1-6. Additive (E)

Various additives may be added to the photosensitive composition of the present invention to improve coating uniformity, adhesiveness, transparency, resolution, flatness, and chemical resistance. Examples of the additives include coupling agents such as anionic, cationic, nonionic, fluorine or silicon leveling agents / surfactants and silane coupling agents, antioxidants such as hindered phenol, hindered amine, phosphorus, , A molecular weight modifier, and an epoxy curing agent.

1-6-1. Surfactants

A surfactant may be added to the photosensitive composition of the present invention to improve coating uniformity. Specific examples of the surfactant include polyphore No. 45, polyflow KL-245, polyflow No. 75, poly flow No. 90, poly flow No. 95 (both trade names, manufactured by Kyoeisha Chemical Co., Ltd.) DisperBak 161, Disper Bak 162, Disper Bake 163, Disper Bake 164, Disper Bake 166, Disper Bake 170, Disper Bake 180, Disper Bake 181, Disper Bake 182, BYK-300, BYK KP-341, KP (trade name), BYK-310, BYK-320, BYK-330, BYK-342, BYK-346, BYK- Surflon-SC-101, Surfron-KH-40, Surflon-S611 (all trade names, manufactured by Shin-Etsu Chemical Industry Co., Ltd.), KF-96-50CS, KF- (Trade names, manufactured by AGC SEIMI CHEMICAL CO., LTD.), FotGent 222F, FotGent 208G, FotGent 251, FotGent 710FL, FotGent 710FM, FotGent 710FS, FotGent 601AD, FotGent 602A, FotGent 650A, FTX-218 All brand names; (All trade names: Mitsubishi F-171, Megafac F-177, EFTOP EF-801, EFTOP EF-801, EFTOP EF-351, EFTOP EF-351, EFTOP EF- MegaPark F-552, MegaPark F-553, MegaPark F-473, MegaPark F-475, MegaPark F-552, MegaPark F- MEGA PARK F-554, MEGA PARK F-555, MEGA PARK F-556, MEGA PARK F-558, MEGA PARK F-559, MEGA PARK R- TEGO Twin 4100, TEGO Flow 370, TEGO Glide 420, TEGO Glide 440, TEGO Glide 450, TEGO Glide 420, Rad 2200N, TEGO Rad 2250N (all trade names, Ebonic Degussa Japan KK), fluoroalkylbenzenesulfonic acid salts, fluoroalkylcarboxylic acid salts, fluoroalkylpolyoxyethylene ethers, fluoroalkylammonium iodides, fluoroalkyl Betaine, fluoroalkylsulfonic acid salt, diglycerin tetrakis Polyoxyethylene nonylphenyl ether, polyoxyethylene octylphenyl ether, polyoxyethylene alkyl ether, polyoxyethylene lauryl ether, polyoxyethylene lauryl ether, polyoxyethylene lauryl ether, and polyoxyethylene lauryl ether. Polyoxyethylene stearyl ether, polyoxyethylene stearyl ether, polyoxyethylene laurate, polyoxyethylene oleate, polyoxyethylene stearate, polyoxyethylene lauryl amine, polyoxyethylene stearyl ether, polyoxyethylene stearyl ether, , Sorbitan laurate, sorbitan palmitate, sorbitan stearate, sorbitan oleate, sorbitan fatty acid ester, polyoxyethylene sorbitan laurate, polyoxyethylene sorbitan palmitate, polyoxyethylene sorbitan stearate, Polyoxyethylene sorbitan oleate, polyoxyethylene Naphthyl ether, alkylbenzenesulfonic acid salts, and alkyl diphenyl ether disulfonic acid salts. It is preferable to use at least one selected from these.

Among these surfactants, mention may be made of BYK-306, BYK-342, BYK-346, KP-341, KP-358, KP-368, Surfron-S611, Fotogent 710FL, Fotogent 710FM, Fotogent 710FS, , Megafac RS-72-K, Megafac DS-21, TEGO Twin 4000, fluoroalkylbenzenesulfonic acid salts, fluoroalkylsulfonic acid salts such as < RTI ID = 0.0 & At least one selected from the group consisting of a carboxylate, a fluoroalkyl polyoxyethylene ether, a fluoroalkylsulfonate, a fluoroalkyltrimethylammonium salt, and a fluoroalkylaminosulfonate is preferable because the coating uniformity of the photosensitive composition is enhanced .

The content of the surfactant in the photosensitive composition of the present invention is preferably 0.01 to 10% by weight based on the total amount of the photosensitive composition.

1-6-2. Coupling agent

The photosensitive composition of the present invention may further contain a coupling agent from the viewpoint of further improving the adhesion between the cured film to be formed and the substrate.

As such a coupling agent, for example, a silane-based, aluminum-based or titanate-based coupling agent can be used. Specific examples thereof include 3-glycidyloxypropyldimethylethoxysilane, 3-glycidyloxypropylmethyldiethoxysilane, 3-glycidyloxypropyltrimethoxysilane (for example, trade name: Sara Ace S510 , JNC Co., Ltd.), 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane (trade name: Sara Ace S530, JNC Co., Ltd.), 3-mercaptopropyltrimethoxysilane Silane coupling agents such as a copolymer of 3-glycidyl-oxypropyl-trimethoxysilane (for example, trade name: CoatOSil MP200, Momentive Performance Materials Co., Ltd.) An aluminate coupling agent such as a coupling agent, an aliphatic coupling agent and an acetal alkoxy aluminum diisopropylate, and a titanate coupling agent such as tetraisopropyl bis (dioctylphosphite) titanate.

Among them, 3-glycidyloxypropyltrimethoxysilane is preferable because it has a large effect of improving the adhesion.

The content of the coupling agent is preferably 0.01 wt% or more and 10 wt% or less with respect to the total amount of the photosensitive composition, because adhesion between the cured film and the substrate is improved.

1-6-3. Antioxidant

The photosensitive composition of the present invention may further contain an antioxidant in order to improve transparency and prevent yellowing when the cured film is exposed to high temperatures.

Antioxidants such as hindered phenol-based, hindered amine-based, phosphorus-based, and sulfur-based compounds may be added to the photosensitive composition of the present invention. Among them, the hindered phenol system is preferable from the viewpoint of weather resistance. Concrete examples are, Irganox1010, Irganox1010FF, Irganox1035, Irganox1035FF, Irganox1076, Irganox1076FD, Irganox1076DWJ, Irganox1098, Irganox1135, Irganox1330, Irganox1726, Irganox1425 WL, Irganox1520L, Irganox245, Irganox245FF, Irganox245DWJ, Irganox259, Irganox3114, Irganox565, Irganox565DD, Irganox295 (all trade names ; ADK STAB AO-20, ADK STAB AO-30, ADK STAB AO-50, ADK STAB AO-60, ADK STAB AO-70 and ADK STAB AO-80 . Of these, Irganox 1010 and ADK STAB AO-60 are more preferable.

The antioxidant is used in an amount of 0.1 to 10 parts by weight based on the total amount of the photosensitive composition.

1-6-4. Molecular weight regulator

The photosensitive composition of the present invention may further contain a molecular weight adjuster in order to suppress the increase in molecular weight by polymerization and to exhibit excellent resolution. Examples of the molecular weight adjusting agent include mercaptans, xanthogens, quinones, and 2,4-diphenyl-4-methyl-1-pentene.

Specific examples of the molecular weight regulator include 2-hydroxy-1,4-naphthoquinone, benzoquinone, 1,4-naphthoquinone, 1,4-dihydroxynaphthalene, 2,5- A hydroquinone, a hydroquinone, a methylhydroquinone, a t-butylhydroquinone, a methoquinone, a p-benzoquinone, a methyl-p-benzoquinone, , n-dodecyl mercaptan, t-dodecyl mercaptan, thioglycolic acid, dimethyl xanthogen sulfide, diisopropyl xanthogen disulfide, 2,4-diphenyl- .

The molecular weight modifier may be used alone or in combination of two or more. Among the molecular weight modifiers, a naphthoquinone molecular weight modifier is preferred from the viewpoint of exhibiting excellent resolution.

Among the molecular weight regulators, 2-hydroxy-1,4-naphthoquinone having a phenolic hydroxyl group is more preferred from the viewpoint of resolution. It is preferable that the content of the photopolymerization initiator (C) is more than 5.0 times and the content of the photopolymerization initiator (C) is less than 30 times as much as the content of the molecular weight regulator And more preferably 20 times or less the molecular weight regulator. It is more preferable that the content of the photopolymerization initiator (C) is more than 5.2 times the content of the molecular weight modifier, and the molecular weight regulator is contained so as to be 10 times or less.

1-6-5. Epoxy hardener

The photosensitive composition of the present invention may further contain an epoxy curing agent to improve flatness and chemical resistance. Examples of the epoxy curing agent include an acid anhydride type curing agent, an amine type curing agent, a phenol type curing agent, an imidazole type curing agent, a catalyst type curing agent and a thermosensitive acid generator such as a sulfonium salt, a benzothiazolium salt, an ammonium salt and a phosphonium salt , An acid anhydride-based curing agent or an imidazole-based curing agent is preferable from the standpoint of avoiding coloring of the cured film and the heat resistance of the cured film.

Specific examples of the acid anhydride-based curing agent include aliphatic dicarboxylic acid anhydrides such as maleic anhydride, tetrahydrophthalic acid anhydride, hexahydrophthalic anhydride, methylhexahydrophthalic acid anhydride, and hexahydrotrimellitic anhydride, And polycarboxylic acid anhydrides such as phthalic anhydride and trimellitic anhydride. Among them, trimellitic acid anhydride and hexahydrotrimellitic acid anhydride which can improve the heat resistance of the cured film without deteriorating the solubility of the photosensitive composition in a solvent are particularly preferable.

Specific examples of the imidazole-based curing agent include 2-undecylimidazole, 2-heptadecylimidazole, 2-phenylimidazole, 2-phenyl-4-methylimidazole, -1H-pyrrolo [1,2-a] benzimidazole, and 1-cyanoethyl-2-undecylimidazolium trimellitate. Of these, 2-undecylimidazole is particularly preferable, which does not impair the solubility of the photosensitive composition in a solvent and can improve the curability of the cured film.

The ratio of the epoxy curing agent to the epoxy compound (D) is 0.1 to 60 parts by weight of the epoxy curing agent relative to 100 parts by weight of the epoxy compound (D). For example, the addition amount of the epoxy curing agent in the case of an acid anhydride-based curing agent is preferably such that the amount of the carboxylic acid anhydride group or the carboxyl group in the epoxy curing agent is 0.1 to 1.5 times the equivalent of the epoxy group. At this time, the carboxylic acid anhydride group is calculated in two dimensions. The carboxylic acid anhydride group or the carboxyl group is preferably added in an amount of 0.15 to 0.8 times the equivalent amount because the chemical resistance is further improved.

1-6-6. Ultraviolet absorber

The photosensitive composition of the present invention may contain an ultraviolet absorber from the viewpoint of further improving the ability of the patterned transparent film to prevent deterioration.

Specific examples of the ultraviolet absorber include TINUVIN P, TINUVIN 120, TINUVIN 144, TINUVIN 213, TINUVIN 234, TINUVIN 326, TINUVIN 571, and TINUVIN 765 (all trade names, BASF Japan Co., Ltd.).

The ultraviolet absorber is used in an amount of 0.01 to 10 parts by weight based on the total amount of the photosensitive composition.

1-6-7. Anti-aggregation agent

The photosensitive composition of the present invention may contain an anti-aggregation agent from the viewpoint of making the solid content intimate with the solvent and preventing agglomeration.

Specific examples of the antiflocculating agent include Disperbyk-145, Disperfect-161, Disperfect-162, Disperfect-163, Disperfect-164, Disperfect-182, 184, DISPERBAKE-185, DISPERBEQUE-2163, DISPERBEQUE-2164, BYK-220S, DISPERBEQUE-191, DISPERBEQUE-199, DISPERBEQUE-2015 ), FTX-218, Ftergent 710FM, Ftergent 710FS (all trade names, Neos), Floren G-600 and Floren G-700 (all trade names, Kyoeisha Chemical Co., Ltd.).

The coagulation inhibitor is added in an amount of 0.01 to 10 parts by weight based on the total amount of the photosensitive composition.

1-6-8. Thermal crosslinking agent

The photosensitive composition of the present invention may contain a heat crosslinking agent in view of further improving heat resistance, chemical resistance, uniformity in film plane, flexibility, flexibility and elasticity.

Specific examples of the thermal crosslinking agent include NIKARAK MW-30HM, NIKARAK MW-100LM, NIKARAK MW-270, NIKARAK MW-280, NIKARAK MW-290, NIKARAK MW-390, (Trade name; Sanwa Chemical Co., Ltd.).

The heat crosslinking agent is used in an amount of 0.1 to 10 parts by weight based on the total amount of the photosensitive composition.

1-6-9. Photoacid generator

The photosensitive composition of the present invention may contain a photoacid generator from the viewpoint of improving the resolution. As the photoacid generator, a 1,2-quinonediazide compound is used.

Specific examples of the 1,2-quinonediazide compound include 2,3,4-trihydroxybenzophenone-1,2-naphthoquinonediazide-4-sulfonic acid ester, 2,3,4-trihydroxybenzo 2-naphthoquinonediazide-5-sulfonic acid ester, 2,4,6-trihydroxybenzophenone-1,2-naphthoquinonediazide-4-sulfonic acid ester, 2,4,6- Trihydroxybenzophenone-1,2-naphthoquinonediazide-5-sulfonic acid ester;

2,2 ', 4,4'-tetrahydroxybenzophenone-1,2-naphthoquinonediazide-4-sulfonic acid ester, 2,2', 4,4'-tetrahydroxybenzophenone-1,2 -Naphthoquinonediazide-5-sulfonic acid ester, 2,3,3 ', 4-tetrahydroxybenzophenone-1,2-naphthoquinonediazide-4-sulfonic acid ester, 2,3,3', 4 -Tetrahydroxybenzophenone-1,2-naphthoquinonediazide-5-sulfonic acid ester, 2,3,4,4'-tetrahydroxybenzophenone-1,2-naphthoquinonediazide-4-sulfonic acid Ester, 2,3,4,4'-tetrahydroxybenzophenone-1,2-naphthoquinonediazide-5-sulfonic acid ester;

Bis (2,4-dihydroxyphenyl) methane-1,2-naphthoquinonediazide-4-sulfonic acid ester, bis (2,4-dihydroxyphenyl) methane-1,2-naphthoquinonediazide -5-sulfonic acid ester;

Bis (p-hydroxyphenyl) methane-1,2-naphthoquinonediazide-4-sulfonic acid ester, bis (p-hydroxyphenyl) methane-1,2-naphthoquinonediazide-5-sulfonic acid ester;

Tri (p-hydroxyphenyl) methane-1,2-naphthoquinonediazide-5-sulfonic acid ester, tri (p-hydroxyphenyl) methane- (P-hydroxyphenyl) ethane-1,2-naphthoquinonediazide-4-sulfonic acid ester, 1,1,1-tri -Naphthoquinonediazide-5-sulfonic acid ester;

Bis (2,3,4-trihydroxyphenyl) methane-1,2-naphthoquinonediazide-4-sulfonic acid ester, bis (2,3,4-trihydroxyphenyl) methane- (2,3,4-trihydroxyphenyl) propane-1,2-naphthoquinonediazide-4-sulfonic acid ester, 2,2-bis 2,3,4-trihydroxyphenyl) propane-1,2-naphthoquinonediazide-5-sulfonic acid ester;

(2,5-dimethyl-4-hydroxyphenyl) -3-phenylpropane-1,2-naphthoquinonediazide-4-sulfonic acid ester, 1,1,3-tris , 5-dimethyl-4-hydroxyphenyl) -3-phenylpropane-1,2-naphthoquinonediazide-5-sulfonic acid ester;

Methylphenyl] ethylidene] bisphenol-1,2-naphthoquinonediazide-4-sulfonic acid ester, 4,4'- [1- [4- [1- [4- hydroxyphenyl] , 4 '- [1- [4- [1- [4-hydroxyphenyl] -1-methylethyl] phenyl] ethylidene] bisphenol-1,2-naphthoquinonediazide-5-sulfonic acid ester;

Bis (2,5-dimethyl-4-hydroxyphenyl) -2-hydroxyphenylmethane-1,2-naphthoquinonediazide-4-sulfonic acid ester, bis (2,5- ) -2-hydroxyphenylmethane-1,2-naphthoquinonediazide-5-sulfonic acid ester;

3,3,3 ', 3'-tetramethyl-1,1'-spirobindene-5,6,7,5', 6 ', 7'-hexanol-l, 2-naphthoquinonediazide- Sulfonic acid ester, 3,3,3 ', 3'-tetramethyl-1,1'-spirobindene-5,6,7,5', 6 ', 7'-hexanol- Toquinonediazide-5-sulfonic acid ester;

2,2,4-trimethyl-7,2 ', 4'-trihydroxyflagane-1,2-naphthoquinonediazide-4-sulfonic acid ester and 2,2,4-trimethyl- , 4'-trihydroxyplazane-1,2-naphthoquinonediazide-5-sulfonic acid ester.

The photoacid generator is added in an amount of 0.01 to 10 parts by weight based on the total amount of the photosensitive composition.

1-6-10. Other additives

The photosensitive composition of the present invention comprises a radical polymerizable compound (P1) represented by the following formula (6), a radically polymerizable compound (P2) having an alkoxysilyl, and a radical polymerizable compound having at least one of epoxy, carboxyl and hydroxyphenyl (Hereinafter also referred to as " radical copolymerization polymer ") by radical copolymerization of the compound (P3).

In the formula (6), R ⁵ is hydrogen or methyl, R ⁶ ~R ⁹ is an alkyl having a carbon number of 1~5, R ¹⁰ is an alkyl having a carbon number of 1~10, m is an integer of 1~10, n Is an integer of 1 to 150.

1-6-10-1. The radical polymerizing compound (P1)

Since the radical polymerizable compound (P1) represented by the formula (6) functions as a surfactant, the use of the (P1) as a raw material enables the radical copolymeric polymer to act as a surfactant, and even if no surfactant is added, , The adhesion to the substrate and the coating ability are improved. By adding the radical polymerizing compound (P1), the radical copolymer polymer tends to be present on the surface of the film.

In the present invention, in the radical polymerizable compound (P1) represented by the formula (6), R ⁸ is hydrogen or methyl, R ⁹ to R ¹² are methyl, R ¹³ is alkyl having 1 to 10 carbon atoms, m is 1 to 5 And n is an integer of 1 to 150, are preferable. R ⁸ is methyl, R ⁹ to R ¹² are methyl, R ¹³ is butyl, m is 3, and n is an integer of 1 to 150, and more preferably n is an integer of 30 to 70, and n Is particularly preferably an integer of 50 to 70. [ The weight average molecular weight of the radically polymerizable compound (P1) represented by the formula (6) is preferably 500 to 8000.

The radical polymerizable compound (P1) can be produced by a known method. A commercially available one may also be used. For example, FM-0711, FM-0721, and FM-0725 (trade names, all manufactured by JNC Co., Ltd.).

1-6-10-2. The radically polymerizable compound (P2) having alkoxysilyl

In the present invention, a radically polymerizable compound (P2) having alkoxysilyl is used as a raw material for obtaining the radical copolymer polymer. Preferred radically polymerizable compounds (P2) are 3- (meth) acryloxypropyltrimethoxysilane, 3- (meth) acryloxypropyltriethoxysilane, 3- (meth) acryloxypropylmethyldimethoxysilane, 3 - (meth) acryloxypropylmethyldiethoxysilane, vinyltrimethoxysilane, vinyltriethoxysilane, p-styryltrimethoxysilane, and the like. Among them, 3- (meth) acryloxypropyltrimethoxysilane and 3- (meth) acryloxypropyltriethoxysilane are preferred because of their good flatness. (P2) is used, transparency, chemical resistance and the like are improved. Further, the adhesion to the substrate is improved by the silane coupling effect.

1-6-10-3. A radically polymerizable compound (P3) having at least one of epoxy, carboxyl and hydroxyphenyl,

In the present invention, a radically polymerizable compound (P3) having at least one of epoxy, carboxyl and hydroxyphenyl is used as a raw material for obtaining the radical copolymer polymer. The preferred radically polymerizable compound (P3) is selected from the group consisting of glycidyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate glycidyl ether, (meth) acrylic acid and 4-hydroxyphenyl vinyl ketone One or more selected. (P3) functions as a crosslinking agent for the polymer and contributes to improvement of heat resistance, chemical resistance and the like.

1-6-10-4. Method for producing radical copolymerizable polymer

The radical copolymeric polymer is obtained by reacting a radical polymerizable compound (P1) represented by the formula (6), a radically polymerizable compound (P2) having an alkoxysilyl and a radically polymerizable compound having at least one of epoxy, carboxyl and hydroxyphenyl P3). ≪ / RTI > The method for producing the radical copolymerization polymer is not particularly limited, but the radical copolymerization polymer can be prepared by heating the above-mentioned radical polymerizable compounds in the presence of a radical initiator. As the radical initiator, organic peroxides, azo compounds and the like can be used. The reaction temperature of the radical copolymerization is not particularly limited, but is usually in the range of 50 to 150 캜. The reaction time is not particularly limited, but is usually in the range of 1 to 48 hours. Further, the reaction can be carried out under any pressure of pressure, reduced pressure or atmospheric pressure.

The solvent used in the radical copolymerization reaction is preferably a solvent in which the resulting polymer is dissolved. Specific examples of the solvent include ethyl acetate, butyl acetate, propyl acetate, butyl propionate, ethyl lactate, methyl methoxyacetate, ethyl methoxyacetate, butyl methoxyacetate, ethyl ethoxyacetate, Methyl propionate, ethyl 3-hydroxypropionate, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, methyl 2-hydroxypropionate, Methyl propionate, methyl 2-methoxypropionate, methyl 2-methoxypropionate, ethyl 2-methoxypropionate, propyl 2-methoxypropionate, methyl 2-ethoxypropionate, Methyl propionate, ethyl 2-ethoxy-2-methylpropionate, methyl pyruvate, ethyl pyruvate, propyl pyruvate, methyl acetonate, ethyl acetonate, 2- Methyl oxobutanoate, 2- Propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol monopropyl ether acetate, propylene glycol monomethyl ether acetate, propylene glycol monomethyl ether acetate, , Ethylene glycol monobutyl ether acetate, cyclohexanone, cyclopentanone, diethylene glycol monomethyl ether, diethylene glycol monomethyl ether acetate, diethylene glycol monoethyl ether, diethylene glycol monoethyl ether acetate, diethylene glycol mono Butyl ether, diethylene glycol monobutyl ether acetate, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, and diethylene glycol methyl ethyl ether. One of these solvents may be used as the solvent, or a mixture of two or more of them may be used.

The radical copolymerization polymer used in the present invention may be a radical copolymerization polymer solution in which the solvent used for the polymerization is left as it is, taking into account the handling property, etc., and the solvent may be removed to obtain a solid radical copolymer polymer in consideration of transportability and the like.

Radical copolymerized polymers are preferred because they have good film-forming properties when the weight average molecular weight determined by GPC analysis using polystyrene as a standard is in the range of 1,000 to 50,000. When the weight-average molecular weight is in the range of 2,500 to 20,000, the flatness of the cured film is more preferable. Further, if the weight average molecular weight is in the range of 2,500 to 15,000, the flatness and chemical resistance of the cured film are particularly preferable.

The other additives are used in an amount of 0.1 to 20 parts by weight based on the total amount of the photosensitive composition.

1-7. solvent

A solvent may be added to the photosensitive composition of the present invention. The solvent optionally added to the photosensitive composition of the present invention is preferably a solvent capable of dissolving the polyester amide acid (A), the compound (B), the photopolymerization initiator (C), the epoxy compound (D) and the like. Specific examples of the solvent include ethyl acetate, butyl acetate, propyl acetate, butyl propionate, ethyl lactate, methyl methoxyacetate, ethyl methoxyacetate, butyl methoxyacetate, ethyl ethoxyacetate, Methoxypropionate, methyl 3-hydroxypropionate, methyl 3-oxypropionate, ethyl 3-hydroxypropionate, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, Methoxypropionate, methyl 2-hydroxypropionate, methyl 2-methoxypropionate, ethyl 2-methoxypropionate, propyl 2-methoxypropionate, methyl 2-ethoxypropionate, ethyl 2-ethoxypropionate, Methyl propionate, methyl propionate, ethyl 2-hydroxy-2-methyl propionate, methyl 2-methoxy-2-methyl propionate, ethyl 2-ethoxy-2-methyl propionate, methyl pyruvate, ethyl pyruvate, , Ethyl acetoacetate, 2- Propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, propylene glycol monomethyl ether, Propylene glycol monopropyl ether acetate, ethylene glycol monobutyl ether acetate, cyclohexanone, cyclopentanone, diethylene glycol monomethyl ether, diethylene glycol monomethyl ether acetate, diethylene glycol monoethyl ether, diethylene glycol mono Ethyl ether acetate, diethylene glycol monobutyl ether, diethylene glycol monobutyl ether acetate, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, and diethylene glycol methyl ethyl ether. One of these solvents may be used as the solvent, or a mixture of two or more of them may be used.

1-8. Preservation of Photosensitive Compositions

When the photosensitive composition of the present invention is stored in the range of -30 占 폚 to 25 占 폚, the stability of the composition with time is improved. If the storage temperature is -20 占 폚 to 10 占 폚, there is no precipitate, and still more preferable.

2. Curing film of photosensitive composition

The photosensitive composition of the present invention is obtained by mixing a polyester amide acid (A), a compound (B), a photopolymerization initiator (C), an epoxy compound (D) and an additive (E) And then homogeneously mixing and dissolving them. As the additive (E), a coupling agent, a surfactant, and other additives may be selected and used depending on the intended characteristics.

When the photosensitive composition prepared as described above (after dissolving in a solvent in a solid state without solvent) is applied to the substrate surface and the solvent is removed, for example, by heating, the coating film can be formed. The application of the photosensitive composition to the surface of the substrate can be carried out by a conventionally known method such as a spin coating method, a roll coating method, a dipping method, a flexo printing method, a spraying method and a slit coating method. Subsequently, this coating film is heated (prebaked) on a hot plate, an oven or the like. The heating conditions differ depending on the kind of each component and the mixing ratio, but it is usually 70 to 150 ° C, 5 to 15 minutes in the case of an oven, and 1 to 5 minutes in the case of a hot plate.

Thereafter, ultraviolet rays are irradiated to the coated film through a mask of a desired pattern shape. The amount of ultraviolet radiation is suitably 5 to 1000 mJ / cm 2 by i-line. The photosensitive composition to which ultraviolet light is irradiated becomes a three-dimensional crosslinked product by polymerization of a compound having a polymerizable double bond, and is insoluble in an alkali developing solution.

Subsequently, the coating film is immersed in an alkali developing solution by a shower phenomenon, a spray phenomenon, a puddle phenomenon, a dip phenomenon, or the like, and an unnecessary portion is dissolved and removed. Specific examples of the alkali developing solution include aqueous solutions of inorganic alkalis such as sodium carbonate, sodium hydroxide, and potassium hydroxide, and aqueous solutions of organic alkalis such as tetramethylammonium hydroxide and tetraethylammonium hydroxide. In addition, an appropriate amount of methanol, ethanol, and a surfactant may be added to the alkali developing solution.

Finally, in order to completely cure the coating film, a cured film can be obtained by heating at 180 to 250 캜, preferably 200 to 250 캜, for 30 to 90 minutes for an oven and for 5 to 30 minutes for a hot plate.

The cured film thus obtained is further subjected to heat treatment at the time of heating in such a manner that 1) the polyamic acid portion of the polyester amide acid (A) is dehydrated and cyclized to form an imide bond, 2) the carboxylic acid of the polyester amide acid is an epoxy group Containing polymer to have a high molecular weight, it is very strong and has excellent transparency, heat resistance, chemical resistance, flatness, adhesion, light resistance and resistance to mist. Therefore, the cured film of the present invention is effective when used as a protective film for a color filter, and a liquid crystal display element or a solid-state imaging element can be manufactured using a color filter. The cured film of the present invention is effective when used as a transparent insulating film formed between a TFT and a transparent electrode, or a transparent insulating film formed between a transparent electrode and an oriented film, in addition to a protective film for a color filter. Further, the cured film of the present invention is also effective as a protective film for an LED light-emitting body.

Example

Next, the present invention will be described concretely by way of Synthesis Examples, Examples and Comparative Examples, but the present invention is not limited at all by these Examples. First, a polyester amide acid solution comprising a reaction product of tetracarboxylic acid dianhydride, diamine, monohydroxy compound, polyhydric hydroxy compound and the like was synthesized as shown below (Synthesis Examples 1 to 17).

[Synthesis Example 1] Synthesis of polyester amide acid solution (A1)

In a four-necked flask equipped with a stirrer, propylene glycol monomethyl ether acetate (PGMEA), 1,2,3,4-butanetetracarboxylic acid dianhydride (BT-100) and SMA1000P (trade name: styrene- maleic anhydride copolymer (Trade name, acrylic acid modified product of propylene glycol diglycidyl ether, Kyohei Kagaku Co., Ltd.) in the following order, and the mixture was stirred at 125 ° C in a dry nitrogen stream And the mixture was stirred for 2 hours (synthesis step 1).

PGMEA  42.79 g

BT-100   2.76 g

SMA1000P  13.16 g

Benzyl alcohol     4.02 g

Epoxy ester 70PA   3.09 g

Thereafter, the reaction solution was cooled to 25 DEG C and 3,3'-diaminodiphenylsulfone (DDS) and PGMEA were added thereto at the following weights, followed by stirring at 20 to 30 DEG C for 2 hours and then at 125 DEG C for 1 hour (Synthetic second step).

DDS   0.87 g

PGMEA  12.99 g

[Z / Y = 2.7, (Y + Z) /X=0.9]

The solution was cooled to room temperature to obtain a 30 wt% solution (A1) of light yellow transparent polyester amide acid. A portion of the solution was sampled and the weight average molecular weight was determined by GPC analysis (polystyrene standard). As a result, the obtained polymer (A1) had a weight average molecular weight of 6,700.

[Synthesis Examples 2 to 17] Synthesis of polyester amide acid solutions (A2 to A17)

Each component was reacted at the temperature, time and ratio (unit: g) shown in Tables 1-1 to 1-3 in accordance with the method of Synthesis Example 1 to obtain a polyester amide acid solution.

Here, for the names in Tables 1-1 to 1-3, MMP is methyl 3-methoxypropionate, PGMEA is propylene glycol monomethyl ether acetate, ODPA is 3,3 ', 4,4'-diphenyl ether tetra Carboxylic acid dianhydride, CHDMMA, and epoxy ester 80MFA, an acrylic acid-modified product of glycerin polydiglycidyl ether (trade name, manufactured by Kyoeisha Chemical Co., Ltd.) and an epoxy ester 3002A (N) of propylene oxide-modified bisphenol A diglycidyl ether Acrylic acid modified product (trade name, manufactured by Kyoeisha Chemical Co., Ltd.).

[Table 1-1]

[Table 1-2]

[Table 1-3]

[Comparative Synthesis Examples 1 to 4] Synthesis of polyester amide acid solutions (a1 to a4)

Each component was reacted at the temperature, time and ratio (unit: g) shown in Table 2 in accordance with the method of Synthesis Example 1 to obtain a polyester amide acid solution.

[Table 2]

[Example 1]

As shown in Tables 3-1 to 3-3, a 500 ml separable flask equipped with a stirring wing was purged with nitrogen, 100.00 g of the polyester amide acid solution (A1) obtained in Synthesis Example 1 (poly 18.0 g of Aronix M-402 (trade name: Toa Gosei Co., Ltd.) as the compound (B) having a polymerizable double bond other than the polyester amide acid (A) , 3.00 g of NCI-930 as a photopolymerization initiator, 6.00 g of VG3101L as an epoxy compound, 9.00 g of EHPE-3150 and 3 g of glycidoxypropyltrimethoxysilane (trade name: Sara Ace S510 , JNC Co., Ltd.), 162.09 g of MMP dehydrated and purified as a solvent, and 37.47 g of PGMEA were charged and stirred for 3 hours at room temperature to dissolve uniformly. Then, 0.84 g of Megapac RS-72-K (trade name; DIC Co., Ltd.) was added thereto, stirred at room temperature for 1 hour, and filtered through a membrane filter (0.2 탆) to prepare a photosensitive composition.

[Table 3-1]

[Table 3-2]

[Table 3-3]

The photosensitive composition was spin-coated on a glass substrate at 430 rpm for 10 seconds, and pre-baked on a hot plate at 100 DEG C for 2 minutes. Next, light having a wavelength of 350 nm or less is cut out through air using a proximity exposure apparatus TME-150PRC (trade name: Topcon Co., Ltd.), and a g-line (436 nm), h- Line (365 nm) was taken out and exposed. The exposure amount was 30 mJ / cm 2, as measured with a cumulative photometer UIT-102 (trade name, manufactured by Ushio Inc.) and a photodetector UVD-365PD (trade name, manufactured by Ushio Inc.). After the exposure, the coated film was developed with a 0.4 wt% tetramethylammonium hydroxide aqueous solution at 25 캜 for 60 seconds, and then the coated film was cleaned with pure water for 20 seconds, followed by drying on a hot plate at 100 캜 for 2 minutes. Further, post-baking was performed in an oven at 230 캜 for 30 minutes to obtain a glass substrate on which a cured film having a thickness of 1.5 탆 was formed.

As shown in Tables 5-1 to 5-3, the properties of the cured film thus obtained were evaluated for the remaining film ratio after development, heat resistance, transparency, resolution and flatness.

[Evaluation method of residual film ratio after development]

The film thickness after development and the film thickness after development were measured using a step, surface roughness and fine shape measuring device (trade name: P-16, KLA TENCOR Co., Ltd.), and the residual film ratio after development (film thickness after development × 100 / Thickness) was calculated. The case where the residual film ratio after development was 80% or more was rated as?, The case where the residual film ratio after development was 75% or more was evaluated as?, And the case where the residual film ratio after development was less than 75% was evaluated as x.

Here, pre-development means after pre-baking, and means after cleaning and drying.

[Evaluation method of heat resistance]

The glass substrate on which the obtained cured film was formed was reheated at 230 DEG C for one hour, and then the film thickness before heating and the film thickness after heating were measured and the retention rate was calculated by the following calculation expression. P-16 was used to measure the film thickness. A case where the residual film ratio after heating was 95% or more was evaluated as & cir & and a case where the residual film ratio after heating was less than 95% was evaluated as x.

Remaining film ratio = (film thickness after heating / film thickness before heating) x 100

[Evaluation method of transparency]

In the glass substrate on which the obtained cured film was formed, the transmittance of only the cured film at a wavelength of 400 nm was measured by an ultraviolet visible near infrared spectrophotometer (trade name: V-670, manufactured by Nihon Spectroscope KK). A case where the transmittance was 95% or more was evaluated as?, And a case where the transmittance was less than 95% was evaluated as?.

[Preparation of substrate for evaluation of resolution]

Next, the photosensitive composition was spin-coated on a glass substrate at 430 rpm for 10 seconds and pre-baked on a hot plate at 100 DEG C for 2 minutes. Using a near-field exposure apparatus TME-150PRC through a mask having holes and line patterns of 50 mu m in width in the air, light of 350 nm or less was cut through a wavelength cut filter, and g-line (436 nm) (405 nm) and i-line (365 nm) were taken out and exposed with an exposure gap of 25 탆. The exposure dose was 30 mJ / cm < 2 > as measured with a UV detector UIT-102 and UVD-365PD. After the exposure, the coated film was developed with a 0.4 wt% tetramethylammonium hydroxide aqueous solution at 25 캜 for 60 seconds, and then the coated film was cleaned with pure water for 20 seconds, followed by drying on a hot plate at 100 캜 for 2 minutes. Post baking was performed at 230 캜 for 30 minutes in an oven to obtain a glass substrate on which a patterned cured film having a film thickness of 1.5 탆 was formed.

The cured film thus obtained was evaluated for its resolution.

[Evaluation method of resolution]

The film thickness of the exposed portion of the glass substrate on which the transparent body on the pattern was formed and the depth of the line pattern of 50 mu m width were measured and the resolution was calculated by the following calculation expression. P-16 was used to measure the film thickness and depth. A case where the resolution was 95% or more was evaluated as " ", and a case where the resolution was less than 95% was evaluated as " x ".

Resolution = (depth of line pattern of 50 m width / film thickness of exposed portion) x 100

[Fabrication of substrate for flatness evaluation]

Next, the photosensitive composition was spin-coated at 430 rpm for 10 seconds on a pigment dispersed color filter (hereinafter abbreviated as CF) substrate using a resin black matrix having a maximum step difference of about 0.8 占 퐉, and prebaked on a hot plate at 100 占 폚 for 2 minutes. Subsequently, light having a wavelength of 350 nm or less was cut through a wavelength cut filter to obtain g-line (436 nm), h-line (405 nm), and i-line (365 nm) using a proximity exposure apparatus TME-150PRC Was taken out and exposed. The exposure amount was 30 mJ / cm 2, as measured with a cumulative photometer UIT-102 (trade name, manufactured by Ushio Inc.) and a photoreceptor UVD-365PD (trade name, manufactured by Ushio Inc.). After the exposure, the coated film was developed with a 0.4 wt% tetramethylammonium hydroxide aqueous solution at 25 DEG C for 60 seconds, and then the coated film was washed with pure water for 20 seconds and then dried on a hot plate at 100 DEG C for 2 minutes. Post baking was carried out in an oven at 230 캜 for 30 minutes to obtain CF having a film thickness of 1.5 탆 formed thereon.

The properties of the cured film thus obtained were evaluated in terms of flatness.

[Evaluation method of flatness]

The step on the surface of the cured film of the color filter substrate on which the obtained cured film was formed was measured using a step, surface roughness and fine shape measuring device (trade name: P-16, KLA TENCOR Co., Ltd.). The case where the maximum value of the step difference between the R, G and B pixels including the black matrix (hereinafter abbreviated as the maximum step difference) was less than 0.16 mu m was evaluated as & cir &

[Examples 2 to 17]

Each component was mixed and dissolved in the ratio (unit: g) described in Tables 3-1 to 3-3 according to the method of Example 1 to obtain a photosensitive composition. As to the abbreviations of the additives in Tables 3-1 to 3-3, M-402 represents a compound Aronix M-402 (trade name, manufactured by Toa Gosei Co., Ltd.) having a polymerizable double bond, NCI-930 represents a photopolymerization initiator Adeka Epoxy resin EHPE3150 (trade name, manufactured by Daicel), S510, adhesion promoter SIRIA ACE S510 (trade name, manufactured by Nippon Polyurethane Industry Co., Ltd.) ; RS-72-K is surfactant Megapak RS-72-K (trade name; manufactured by DIC Co.); MMP is methyl 3-methoxypropionate; and PGMEA is solvent propylene glycol monomethyl ether acetate.

[Comparative Examples 1 to 4]

Each component was mixed and dissolved in accordance with the method of Example 1 at the ratio shown in Table 4 (unit: g) to obtain a photosensitive composition.

[Table 4]

The evaluation results of the cured films of Examples 1 to 6 are shown in Table 5-1, the evaluation results of the cured films of Examples 7 to 12 are shown in Table 5-2, the evaluation results of the cured films of Examples 13 to 17 are shown in Table 5- 3, the evaluation results of the cured films of Comparative Examples 1 to 4 are summarized in Table 6, respectively.

[Table 5-1]

[Table 5-2]

[Table 5-3]

[Table 6]

As is clear from the results shown in Tables 5-1 to 5-3, the cured films of Examples 1 to 17 are excellent in heat resistance, transparency and flatness, and have a balance in all points including the residual film ratio and resolution after development You can see that they are caught. On the other hand, as shown in Table 6, all of the cured films of Comparative Examples 1 to 4 had a low residual film ratio after development.

As described above, when a polyester amide acid having a polymerizable double bond obtained by reacting a tetracarboxylic acid dianhydride, a diamine and a polyhydric hydroxy compound as essential raw material components was used, all the characteristics could be satisfied.

Since the cured film obtained from the photosensitive composition of the present invention is excellent in optical characteristics such as heat resistance, transparency, flatness, resolution and residual film ratio, it is preferable to use a protective film of various optical materials such as color filters, LED light emitting devices and light receiving devices, And between the transparent electrode and the transparent electrode and the alignment film.

Claims (19)

A polyester amide acid (A) having a polymerizable double bond,
A compound (B) having a polymerizable double bond other than the polyester amide acid (A)
A composition comprising a photopolymerization initiator (C), an epoxy compound (D) and an additive (E)
The polyester amide acid (A) has a ratio of X mol of tetracarboxylic acid dianhydride, Y mol of diamine and Z mol of polyhydric hydroxy compound in the relationship of the following formulas (1) and (2) ≪ / RTI >
Wherein the compound (B) contains at least two polymerizable double bonds per molecule, the epoxy compound (D) contains 2 to 10 epoxy groups per molecule, the weight average molecular weight is less than 3,000, Wherein the total amount of the compound (B) is 20 to 300 parts by weight based on 100 parts by weight of the ester amide acid (A), and the total amount of the epoxy compound (D) is 20 to 200 parts by weight.
0.2? Z / Y? ... ... (One)
0.2? (Y + Z) /X? 5.0? (2). A polyester amide acid (A) having a polymerizable double bond,
A compound (B) having a polymerizable double bond other than the polyester amide acid (A)
A composition comprising a photopolymerization initiator (C), an epoxy compound (D) and an additive (E)
The polyester amide acid (A) is obtained by reacting X mole of tetracarboxylic acid dianhydride, Y mole of diamine, Z mole of polyhydric hydroxy compound and monohydroxy compound of the following formulas (1) and In a ratio that establishes the relationship,
Wherein the compound (B) contains at least two polymerizable double bonds per molecule, the epoxy compound (D) contains 2 to 10 epoxy groups per molecule, the weight average molecular weight is less than 3,000, Wherein the total amount of the compound (B) is 20 to 300 parts by weight based on 100 parts by weight of the ester amide acid (A), and the total amount of the epoxy compound (D) is 20 to 200 parts by weight.
0.2? Z / Y? ... ... (One)
0.2? (Y + Z) /X? 5.0? (2). The method according to claim 1,
Wherein the polyester amide acid (A) comprises a constituent unit represented by the following formula (3) and a constituent unit represented by the following formula (4)

In the formulas (3) and (4), R ¹ is a residue obtained by removing two -CO-O-CO- from a tetracarboxylic acid dianhydride, R ² is a residue obtained by removing two -NH ₂ from a diamine, R ³ is a residue obtained by removing two -OH from a polyhydric hydroxy compound, and at least one of R ³ has a polymerizable double bond. 3. The method of claim 2,
Wherein the polyester amide acid (A) comprises a constituent unit represented by the following formula (3), a constituent unit represented by the following formula (4), and a constituent unit represented by the following formula (5)

In the formulas (3), (4) and (5), R ¹ is a residue obtained by removing two -CO-O-CO- from a tetracarboxylic acid dianhydride and R ² is a residue obtained by removing two -NH ₂ R ³ is a residue obtained by removing two -OH from a polyhydric hydroxy compound, R ⁴ is a residue obtained by removing one -OH from a monohydroxy compound, and at least one of R ³ and R ⁴ is a residue obtained by polymerizing And has a double bond. 3. The method of claim 2,
Wherein the polyester amide acid (A) comprises a constituent unit represented by the following formula (3), a constituent unit represented by the following formula (4), and a constituent unit represented by the following formula (5)

In the formulas (3), (4) and (5), R ¹ is a residue obtained by removing two -CO-O-CO- from a tetracarboxylic acid dianhydride and R ² is a residue obtained by removing two -NH ₂ R ³ is a residue obtained by removing two -OH from a polyhydric hydroxy compound, R ⁴ is a residue obtained by removing one -OH from a monohydroxy compound, and at least one of R ³ is a polymerizable double bond Respectively. 3. The method of claim 2,
Wherein the polyester amide acid (A) comprises a constituent unit represented by the following formula (3), a constituent unit represented by the following formula (4), and a constituent unit represented by the following formula (5)

In the formulas (3), (4) and (5), R ¹ is a residue obtained by removing two -CO-O-CO- from a tetracarboxylic acid dianhydride and R ² is a residue obtained by removing two -NH ₂ R ³ is a residue obtained by removing two -OH from a polyhydric hydroxy compound, R ⁴ is a residue obtained by removing one -OH from a monohydroxy compound, and at least one of R ⁴ is a polymerizable double bond Respectively. 6. The method according to any one of claims 1 to 5,
The polyhydric hydroxy compound may be at least one compound selected from the group consisting of ethylene glycol, propylene glycol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, 1,7-heptanediol, Bis (4-hydroxycyclohexyl) propane, 4,4'-dihydroxydicyclohexyl, isocyanuric acid tris (2-hydroxyethyl), 2-hydroxybenzyl alcohol, 4-hydroxybenzyl alcohol, 2 - (4-hydroxyphenyl) ethanol, and a polyhydric hydroxy compound having a polymerizable double bond, the polyhydroxy compound having a polymerizable double bond. The method according to claim 6,
The polyhydric hydroxy compound may be at least one compound selected from the group consisting of ethylene glycol, propylene glycol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, 1,7-heptanediol, Bis (4-hydroxycyclohexyl) propane, 4,4'-dihydroxydicyclohexyl, isocyanuric acid tris (2-hydroxyethyl), 2-hydroxybenzyl alcohol, 4-hydroxybenzyl alcohol and And 2- (4-hydroxyphenyl) ethanol. 8. The method of claim 7,
The polyhydroxy compound having a polymerizable double bond has a vinyl group, an allyl group, or a (meth) acryloxy group. 8. The method of claim 7,
The polyhydric hydroxy compound having a polymerizable double bond may be at least one selected from the group consisting of glycerin mono (meth) acrylate, trimethylolpropane mono (meth) acrylate, pentaerythritol mono (meth) acrylate, pentaerythritol di (meth) Acrylate, dipentaerythritol tri (meth) acrylate, dipentaerythritol tetra (meth) acrylate, sorbitol mono (meth) acrylate, dipentaerythritol tri (Meth) acrylic acid modified product of propylene glycol diglycidyl ether, sorbitol di (meth) acrylate, sorbitol tri (meth) acrylate, sorbitol tetra (meth) acrylate, ethylene glycol diglycidyl ether (Meth) acrylic acid modified product, a (meth) acrylic acid modified product of tripropylene glycol diglycidyl ether, a (meth) acrylic acid modified product of glycerin diglycidyl ether (Meth) acrylic acid modified product of bisphenol A diglycidyl ether, a (meth) acrylic acid modified product of propylene oxide-modified bisphenol A diglycidyl ether, and a compound containing two or more epoxy groups per molecule (Meth) acrylic acid modified product, and a (meth) acrylic acid modified product. The method according to claim 2, 4, 5, or 6,
Wherein the monohydroxy compound is at least one selected from the group consisting of isopropyl alcohol, benzyl alcohol, propylene glycol monoethyl ether, 3-ethyl-3-hydroxymethyloxetane, and a monohydroxy compound having a polymerizable double bond ≪ / RTI > 6. The method of claim 5,
Wherein the monohydroxy compound is at least one compound selected from the group consisting of isopropyl alcohol, benzyl alcohol, propylene glycol monoethyl ether, and 3-ethyl-3-hydroxymethyloxetane. 12. The method of claim 11,
Wherein the monohydroxy compound having a polymerizable double bond has a vinyl group, an allyl group, or a (meth) acryloxy group. 12. The method of claim 11,
The monohydroxy compound having a polymerizable double bond may be at least one selected from the group consisting of furfuryl alcohol, hydroxypropyl (meth) acrylate, hydroxybutyl (meth) acrylate, 2-hydroxy- (Meth) acrylate such as 4-hydroxyphenyl (meth) acrylate, p-hydroxy (meth) acrylanilide, 1,4- (Meth) acrylate, trimethylolpropane di (meth) acrylate, pentaerythritol tri (meth) acrylate, dipentaerythritol penta (meth) acrylate, and epoxy groups per molecule (Meth) acrylic acid modified product, and a (meth) acrylic acid modified product. 7. The method according to any one of claims 1 to 6,
Wherein the polyester amide acid (A) has a weight average molecular weight of 1,000 to 200,000. 7. The method according to any one of claims 1 to 6,
The tetracarboxylic acid dianhydride may be selected from the group consisting of 3,3 ', 4,4'-diphenylsulfone tetracarboxylic acid dianhydride, 3,3', 4,4'-diphenylether tetracarboxylic dianhydride, 2,2- [ Bis (3,4-dicarboxyphenyl)] hexafluoropropane dianhydride, 1,2,3,4-butanetetracarboxylic acid dianhydride, and ethylene glycol bis (anhydrotrimellitate) At least one compound,
The diamine is at least one of 3,3'-diaminodiphenylsulfone and bis [4- (3-aminophenoxy) phenyl] sulfone,
The compound (B) may be at least one compound selected from the group consisting of dipentaerythritol pentaacrylate, dipentaerythritol hexaacrylate, pentaerythritol tetraacrylate, pentaerythritol triacrylate, isocyanuric acid ethylene oxide modified triacrylate, and polybasic acid- ) Acrylic oligomer in an amount of at least 50% by weight based on the total weight of the composition,
The epoxy compound (D) can be obtained by reacting 3 ', 4'-epoxycyclohexylmethyl-3,4-epoxycyclohexanecarboxylate, 1-methyl-4- Ethyl] phenyl] phenyl] -2- [4- [1,1-bis [4- (2,3-epoxypropoxy) ] Propane and 1,3-bis [4- [1- [4- (2,3-epoxypropoxy) phenyl] -1- [4- [1- [4- (2,3-epoxypropoxy) phenyl Phenyl] -2- [4- [1, 1 -bis [2, 3-dihydroxyphenyl] Phenylpropane, 1,1,1-tris (4-hydroxyphenyl) ethane triglycidyl ether, 1,3-bis (oxiranylmethyl) - (1H, 3H, 5H) -triene, 2,2-bis (hydroxymethyl) -1- , 2-epoxy-4- (2-oxiranyl) cyclohexane adduct, and the compound is at least one compound selected from the group consisting of 2-
The photopolymerization initiator (C) is at least one selected from the group consisting of an? -Aminoalkylphenone-based, acylphosphine oxide-based, oximeester-based photopolymerization initiator,
Wherein the additive (E) comprises at least one of a coupling agent and a surfactant. 7. The method according to any one of claims 1 to 6,
Wherein the tetracarboxylic dianhydride is at least one of 3,3 ', 4,4'-diphenyl ether tetracarboxylic dianhydride and 1,2,3,4-butanetetracarboxylic dianhydride,
The diamine is 3,3'-diaminodiphenylsulfone,
The compound (B) is at least one selected from the group consisting of dipentaerythritol pentaacrylate, dipentaerythritol hexaacrylate and polybasic acid-modified (meth) acrylic oligomer,
The photopolymerization initiator (C) may be at least one selected from the group consisting of 1,2-octanedione-1- [4- (phenylthio) phenyl] -2- (O-benzoyloxime), ethanone, 1- [ (Methylbenzoyl) -9H-carbazol-3-yl] -, 1- (O-acetyloxime) and 1,2-propanedione- 1- [4- [4- (2-hydroxyethoxy) Phenyl] -2- (O-acetyloxime) in an amount of 50% by weight or more based on the total weight of the photopolymerization initiator,
The epoxy compound (D) can be obtained by reacting the epoxy compound (D) with 2- [4- (2,3-epoxypropoxy) phenyl] -2- [4- [ Phenyl] -1,3-bis [4- [1- [4- (2,3-epoxypropoxy) phenyl] -1- [4- [1- [4- Phenyl] -1-methylethyl] phenyl] ethyl] phenoxy] -2-propanol and 2- [4- (2,3-epoxypropoxy) Bis [4- (2,3-epoxypropoxy) phenyl] ethyl] phenyl] propane,
The additive (E) comprises at least one of a coupling agent and a surfactant,
Wherein the solvent contains at least one selected from the group consisting of methyl 3-methoxypropionate and propylene glycol monomethyl ether acetate. A cured film of the photosensitive composition according to any one of claims 1 to 6. A color filter having the cured film of claim 18 as a transparent protective film.